CN104513696B - A kind of calcium zirconium base octa-polyurea lubricating grease and preparation method thereof - Google Patents
A kind of calcium zirconium base octa-polyurea lubricating grease and preparation method thereof Download PDFInfo
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- 0 CCc1cccc(C*=*C)c1 Chemical compound CCc1cccc(C*=*C)c1 0.000 description 1
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Abstract
The invention discloses a kind of calcium zirconium base octa-polyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, including following components：1 59 weight % calcium zirconium base thickening agent；1 59 weight % polyurea compound；40 95 weight % base oil, wherein, the calcium zirconium base thickening agent is the calcium zirconium soap that generation is reacted by component A, component B and component C, wherein, the component A is higher fatty acids and small molecule inorganic acid and/or the mixture of lower straight aliphatic acid, the component B is the oxide and/or hydroxide of calcium, and the component C is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium, and the polyurea compound is eight polyurea compounds.The invention also discloses the preparation method of calcium zirconium base octa-polyurea lubricating grease and its calcium zirconium base octa-polyurea lubricating grease of preparation.Lubricating grease of the present invention, with more preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of calcium zirconium base octa-polyurea lubricating grease and preparation method thereof.
Background technology
Zirconium belongs to Group IVB as a kind of transition metal, positioned at the 5th cycle.Zirconium-containing compound has excellent lubrication
Effect, is often used as lubricating additive, such as CN101113382 and JP1973038444 add the oxide of zirconium as lubricant
Agent improves abrasiveness；WO2007143414 and US20060063682, which describe zirconium tetrafluoride, to be turned into as wear reducing additive
One of component of lubricant；It is resistance to heavy well that US20060254823 has found that the lubricant containing 2 ethyl hexanoic acid zirconates is shown
Load and abrasion resistance；US20050043189 has found that fluozirconate such as fluorine zirconic acid aluminium can be used in lubricant as oxidation retarder
In；DE102004021812 has found that the inorganic salts such as zirconium carbonate, sulfonic acid zirconium or basic zirconium phosphate are added to inside lubricating grease and can improved
Abrasion resistance.
The patent of zirconium base lubricating grease is prepared using zirconates as thickening agent US4189387, and thickening agent is by organic hypophosphorous acid
Or the reaction of monocarboxylic acid and zirconium hydroxide is made, obtained lubricating grease has a preferable extreme pressure anti-wear, but lubricating grease its
His performance still awaits further raising.
The content of the invention
It is an object of the invention to provide a kind of heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, glue
Body stability and extreme pressure anti-wear are preferable, and cost is low, the simple calcium zirconium base octa-polyurea lubricating grease of preparation technology and its preparation side
Method.
The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：1-59 weight %
Calcium zirconium base thickening agent；1-59 weight % polyurea compound；40-95 weight % base oil, wherein, the calcium zirconium base thickening
Agent is the calcium zirconium soap that generation is reacted by component A, component B and component C, wherein, the component A be higher fatty acids and small molecule without
The mixture of machine acid and/or lower straight aliphatic acid, the component B is the oxide and/or hydroxide of calcium, the component C
For at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide, the polyurea compound is eight polyurea compounds.
The lubricating grease has preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and pole
Wear resistence is pressed, and cost is low, preparation technology is simple.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of calcium zirconium base octa-polyurea lubricating grease, to moisten
On the basis of consistent lubricant weight, including following components：1-59 weight % calcium zirconium base thickening agent；1-59 weight % polyurea compound；40-
95 weight % base oil, wherein, the calcium zirconium base thickening agent is the calcium zirconium soap that generation is reacted by component A, component B and component C,
Wherein, the component A is higher fatty acids and small molecule inorganic acid and/or the mixture of lower straight aliphatic acid, the component B
For the oxide and/or hydroxide of calcium, the component C in oxide, the hydroxide of zirconium and the zirconium alkoxide of zirconium extremely
Few one kind, the polyurea compound is eight polyurea compounds.
Preferably, on the basis of lubricating grease weight, including following components：3-40 weight % calcium zirconium base thickening agent；2-40 weights
Measure % eight polyurea compounds；50-93 weight % base oil.
Preferably, in the calcium zirconium base thickening agent, the mol ratio of calcium and zirconium is 1：0.1-10；More preferably 1：0.25-4.
Preferably, the component C is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, in terms of zirconium, zirconium
Oxide and/or hydroxide and zirconium alkoxide mol ratio be 1：0.1-10；More preferably 1：0.5-5.
Second aspect, the invention provides the preparation method of calcium zirconium base octa-polyurea lubricating grease as described above, this method bag
Include：Calcium zirconium base thickening agent, eight polyurea compounds and part basis oil is well mixed, in 180-230 DEG C of constant temperature refining, add remaining
Base oil is measured, necessary additive is added, obtains finished product.
The third aspect, the invention provides a kind of preparation method of calcium zirconium base octa-polyurea lubricating grease, this method includes：
（1）Component A, component B and component C are mixed in base oil, heat up draining saponification, wherein, the component A is height
The mixture of level aliphatic acid and small molecule inorganic acid and/or lower straight aliphatic acid, the component B for calcium oxide and/or
Hydroxide, the component C is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium；
（2）In step（1）Base oil and diisocyanate are added in gained mixture, diamines, diamines is then sequentially added
Reacted with monoamine；
（3）By step（2）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add
Plus agent, obtain finished product.
Preferably, step（1）In, the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：0.25-4.
Preferably, step（1）In, by the component A and base oil Hybrid Heating to 60-90 DEG C, add component B and component
C, in 90-120 DEG C of draining saponification, wherein, component C for zirconium oxide and/or hydroxide and zirconium alkoxide mixture, with
Zirconium meter, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10, more preferably 1：0.5-5.
Fourth aspect, the invention provides the calcium zirconium base octa-polyurea lubricating grease as made from method as described above.
The calcium zirconium base octa-polyurea lubricating grease of the present invention, compared to zirconium base octa-polyurea lubricating grease, with more preferable heat-resisting quantity, machine
Tool stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear, especially when calcium in lubricating grease and zirconium
Mol ratio be 1：0.25-4；The raw material for preparing the zirconium of calcium zirconium base thickening agent is the oxide and/or hydroxide and alcoxyl of zirconium
The mixture of base zirconium；In terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：During 0.5-5, calcium zirconium
Heat-resisting quantity, mechanical stability, water-resistance and the adhesiveness of base octa-polyurea lubricating grease, colloid stability and extreme pressure anti-wear can
It is greatly improved.Preparation of greases technique of the invention is simple, cost is low, and product quality is stable.The lubricating grease of the present invention
It can be widely used for the bearing lubrication such as high speed, heavy load operating, oil drilling.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of calcium zirconium base octa-polyurea lubricating grease, this lubricating grease simultaneously containing calcium zirconium base thickening agent, with
And eight polyurea compounds that isocyanates and amine reaction are produced.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides calcium zirconium base octa-polyurea lubricating grease, on the basis of lubricating grease weight, including with the following group
Point：1-59 weight % calcium zirconium base thickening agent；1-59 weight % polyurea compound；40-95 weight % base oil, wherein, calcium zirconium
Base thickening agent is the calcium zirconium soap that generation is reacted by component A, component B and component C, wherein, component A is higher fatty acids and small molecule
The mixture of inorganic acid and/or lower straight aliphatic acid, component B is the oxide and/or hydroxide of calcium, and component C is zirconium
At least one of oxide, the hydroxide of zirconium and zirconium alkoxide, the polyurea compound are eight polyurea compounds.
Preferably, on the basis of lubricating grease weight, including following components：3-40 weight % calcium zirconium base thickening agent；2-40 weights
Measure % eight polyurea compounds；50-93 weight % base oil；It is highly preferred that on the basis of lubricating grease weight, including with the following group
Point：5-30 weight % calcium zirconium base thickening agent；2-30 weight % polyurea compound；60-90 weight % base oil.
According to the present invention, although the calcium zirconium base octa-polyurea lubricating grease with said components, you can realize the purpose of the present invention,
I.e. lubricating grease has preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and pole
Wear resistence is pressed, but when in calcium zirconium base thickening agent, the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：During 0.25-4, it can enter
One step improves heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of lubricating grease.Cause
This, in calcium zirconium base thickening agent of the invention, the mol ratio of calcium and zirconium is preferably 1：0.1-10, more preferably 1：0.25-4.
The present inventor has been surprisingly found that under study for action, when the oxide and/or hydroxide and alcoxyl that component C is zirconium
During the mixture of base zirconium, i.e., the raw material of zirconium for zirconium oxide and/or hydroxide and zirconium alkoxide mixture when, one can be entered
Step improves heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of lubricating grease, because
This, component C is preferably the oxide and/or hydroxide of zirconium and the mixture of zirconium alkoxide, wherein, in terms of zirconium, the oxidation of zirconium
The mol ratio of thing and/or hydroxide and zirconium alkoxide is preferably 1：0.1-10, more preferably 1：0.2-8, still more preferably
For 1：0.5-5, can be further in the case of the oxide and/or hydroxide of zirconium and the preferred molar ratio of zirconium alkoxide
Improve heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of lubricating grease.
In the present invention, higher fatty acids can be that carbon number is 8-24, preferably 10-20 straight chain fatty acid or hydroxy aliphatic
At least one of acid, such as laurate, oleic acid, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, it is more excellent
Elect 12- hydroxy stearic acids as.
In the present invention, small molecule inorganic acid is preferably boric acid and/or phosphoric acid, lower straight aliphatic acid can for monoacid or
Binary acid, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, ethanedioic acid, malonic acid, fourth can be selected from
At least one of diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid and dodecanedioic acid.
In the present invention, the mol ratio of higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid is preferably 1：
0.2-10, more preferably 1：0.4-5.
In the present invention, higher fatty acids and H contained by small molecule inorganic acid and/or lower straight aliphatic acid+Molal quantity it
With equal to all neutralize calcium oxide, the hydroxide of calcium, the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxides needed for
H+Molal quantity, but calcium oxide, the hydroxide of calcium, the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide relative to
Higher fatty acids can excess 1-10% with small molecule inorganic acid and/or lower straight aliphatic acid.
In the present invention, the oxide and/or hydroxide of calcium can be CaO, Ca (OH)2；The oxide and/or hydrogen-oxygen of zirconium
Compound is preferably selected from ZrO2、ZrO(OH)2、Zr(OH)4At least one of and their hydrate.ZrO(OH)2Hydrate
Can be the wet hydrogen zirconium oxide of brand-new, it can pass through ZrOX2·8H2O（X is F, Cl, Br or I）Or ZrO (NO3)2·2H2O etc.
React and obtain with alkali, wherein, alkali can be NaOH, KOH, concentrated ammonia liquor etc., preferably ZrOCl2·8H2O and NaOH reacts.
In the present invention, the formula of zirconium alkoxide can be Zr (OR1)4, R1Can be C1-C10 alkyl, preferably C2-C6
Alkyl；It is highly preferred that zirconium alkoxide in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium extremely
Few one kind.
In the present invention, eight polyurea compound preferably has following structure：
Wherein, R1Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-
18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.
Wherein, R2Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can
To be phenylene or biphenylene.
Wherein, R3Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub- cycloalkanes
The carbon number of base can be 6-30, preferably 6-20, R3More preferably In at least
It is a kind of.
Above-mentioned eight polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be with
Prepared according to the CN103060068A methods recorded.
In the present invention, 100 DEG C of kinematic viscosity of base oil are preferably 2-150mm2/ s, more preferably 4-60mm2/ s, base oil
Can be at least one of mineral oil, artificial oil and vegetable oil, artificial oil can be poly ＆ Alpha ,-olefin oil（PAO）, Esters oil,
Alkyl-silicone oil, Fischer-Tropsch synthesis oil etc..
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its
In, the preferred arylamine kind antioxidant of antioxidant accounts for the 0.01-5% of lubricating grease gross weight, preferably 0.1-2.5%, can be diphenylamines,
At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease
The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid
At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil
At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of calcium zirconium base octa-polyurea lubricating grease as described above, this method bag
Include：Calcium zirconium base thickening agent, eight polyurea compounds and part basis oil is well mixed, in 180-230 DEG C of constant temperature refining, add remaining
Base oil is measured, necessary additive is added, obtains finished product.
In the present invention, for calcium zirconium base thickening agent, eight polyurea compounds, base oil and additive as described above, herein not
Repeat again.
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 used
Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil：0.5-5.
For calcium zirconium base thickening agent, it can be reacted and obtained in base oil by component A, component B and component C, wherein, component
A is the mixture of higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid, component B for calcium oxide and/or
Hydroxide, component C is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium.For example, by component A and
Part basis oil Hybrid Heating adds component B and component C to 60-90 DEG C, in 90-120 DEG C of draining saponification, wherein, component C is
The oxide and/or hydroxide and the mixture of zirconium alkoxide of zirconium, in terms of zirconium, the oxide and/or hydroxide and alkane of zirconium
The mol ratio of epoxide zirconium is preferably 1：0.1-10, more preferably 1：0.2-8, is still more preferably 1：0.5-5.
The third aspect, the invention provides a kind of preparation method of calcium zirconium base octa-polyurea lubricating grease, this method includes：
（1）Component A, component B and component C are mixed in base oil, heat up draining saponification, wherein, the component A is height
The mixture of level aliphatic acid and small molecule inorganic acid and/or lower straight aliphatic acid, the component B for calcium oxide and/or
Hydroxide, the component C is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium；
（2）In step（1）Base oil and diisocyanate are added in gained mixture, diamines, diamines is then sequentially added
Reacted with monoamine；
（3）By step（2）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add
Plus agent, obtain finished product.
According to the present invention, calcium zirconium base polyurea grease is prepared while in accordance with the above method, you can realize the purpose of the present invention,
The calcium zirconium base polyurea grease prepared has preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, salt fog resistance
Property, colloid stability and extreme pressure anti-wear, but step（1）In, when the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：
During 0.25-4, heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, the colloid peace of obtained lubricating grease can further improve
Qualitative and extreme pressure anti-wear.Therefore, step of the present invention（1）In, the mol ratio of calcium and zirconium is preferably 1：0.1-10, more preferably 1：
0.25-4。
Step of the present invention（1）In, base oil can be made first to be mixed with component A, can also make base oil first and component B and group
Divide C mixing；Higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid can simultaneously in base oil with component B
React and be dehydrated with component C, dehydration can also be reacted respectively.It is preferred that by base oil and component A Hybrid Heatings to 60-90 DEG C, adding
Component B and component C, heat up draining saponification.
As it was previously stated, the present inventor has been surprisingly found that under study for action, step（1）In, when the oxidation that component C is zirconium
During the mixture of thing and/or hydroxide and zirconium alkoxide, i.e., the raw material of zirconium is the oxide and/or hydroxide and alcoxyl of zirconium
During the mixture of base zirconium, can further improve obtained lubricating grease heat-resisting quantity, mechanical stability, water-resistance and adhesiveness,
Colloid stability and extreme pressure anti-wear, it is therefore preferred that step（1）In, by component A and base oil Hybrid Heating to 60-90
DEG C, add component B and component C, in 90-120 DEG C of draining saponification, wherein, component C for zirconium oxide and/or hydroxide with
The mixture of zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are preferably 1：0.1-
10, more preferably 1：0.2-8, is still more preferably 1：0.5-5.
Step of the present invention（1）In, the total amount and base of higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid
The weight ratio preferably 1 of plinth oil：5-50.
Step of the present invention（1）In, the mol ratio of higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid is excellent
Elect 1 as：0.2-10, more preferably 1：0.4-5.
Higher fatty acids, small molecule inorganic acid and/or lower straight aliphatic acid, the oxide of calcium, the hydroxide of calcium, zirconium
Oxide, the hydroxide of zirconium and zirconium alkoxide as it was previously stated, will not be repeated here.
The oxide of higher fatty acids and small molecule inorganic acid and/or lower straight aliphatic acid and calcium, the hydroxide of calcium,
The mol ratio of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is as it was previously stated, will not be repeated here.
Step of the present invention（2）In, in step（1）Base oil and diisocyanate, are then sequentially added in gained mixture
Diamines, diamines and monoamine are reacted, and are in step（1）Eight polyurea compounds are prepared in gained mixture.
The method of eight polyurea compounds is prepared without particular/special requirement, various methods commonly used in the art can be used.For example,
, can be in step in the present invention（2）Base oil and diisocyanate are added in gained mixture, diamines, 2-8 points of stirring is added
Clock, adds diamines again, stirs 2-8 minute, adds monoamine, stir diisocyanate added by 2-8 minutes, each time, diamines,
The mol ratio of diamines and monoamine is 4:2:1:2.
The diisocyanate structure is OCN-R3- NCO, R3Can be that carbon number is 6-30, preferably
6-20 arlydene, alkylidene or cycloalkylidene, be preferably Deng.
For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), and methyldiphenyl diisocyanate (MDI), 1,6- is sub-
Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng
At least one of.
The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R1-NH2、R1’-NH2, R therein1、R1’Can
To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or
Substituted phenyl, preferably phenyl or C1-C3 alkyl or the phenyl of halogen substitution.It is preferred that monoamine can be selected from aniline, m-chloro
Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.
The diamines can be fatty amine or arylamine, and structural formula is NH2-R2-NH2, R therein2Can be alkylidene or Asia
Aryl, the carbon number of alkylidene can be 2-12, and preferably 2-8, arlydene can be phenylene or biphenylene.It is preferred that diamines can
Be selected from p-phenylenediamine, o-phenylenediamine, the aromatic amine of 4,4- benzidines and/or selected from ethylenediamine, propane diamine, 1,6- oneself two
The straight-chain fatty amine of amine.
Step of the present invention（3）In, first in 100-120 DEG C of constant temperature 10-20 minutes, finally it is warming up to 180-230 DEG C of constant temperature 5-
20 minutes；Base oil is added, treats that temperature is cooled to 80-130 DEG C, necessary additive is added, stirring, takes off circulating filtration, homogenizing
Gas.
Base oil and additive are as it was previously stated, will not be repeated here.
In the present invention, step（1）In base oil used total amount and step（2）In base oil used total amount and step
（3）In base oil used total amount weight ratio preferably 1：0.5-5：0.5-5.
Fourth aspect, present invention also offers calcium zirconium base eight made from the preparation method provided as third aspect present invention
Polyurea grease.
Compared with the calcium zirconium base octa-polyurea lubricating grease as made from the preparation method that second aspect is provided, what the third aspect was provided
Calcium zirconium base octa-polyurea lubricating grease made from preparation method have more preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness,
Colloid stability and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
Embodiment 1
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：ZrOCl2·8H2O（22.5g）；NaOH（6g）；Ethanol zirconium（19g）；Ca(OH)2（2.6g）；12- hydroxyls
Base stearic acid（50g）；Decanedioic acid（18g）；Octadecylamine（6.9g）；Ethylenediamine（2.3g）；MDI（12.8g）；HVI500SN lubricates base
Plinth oil（100 DEG C of kinematic viscosity are 10mm2/ s, 400g）.
By 22.5gZrOCl2·8H2O is dissolved in 140g water, and 80g is contained to the 6g NaOH aqueous solution, is slowly added into above-mentioned
ZrOCl2The aqueous solution in, quick stirring obtains white precipitate, is filtrated to get precipitation, precipitation is washed rear standby with massive laundering.
150g HVI500SN lubricating base oils, 50g12- hydroxy stearic acids and 18g decanedioic acid are added into normal oleosterin kettle
In, stirring is heated to 90 DEG C, by 19g ethanol zirconium, the precipitation of above-mentioned brand-new and 2.6gCa (OH)2It is added thereto, calcium and zirconium rub
You are than being 1：4, in terms of zirconium, the precipitation of brand-new and the mol ratio of ethanol zirconium are 1：1,105 DEG C of draining saponification are warming up to, are warming up to
120℃；50g HVI500SN lubricating base oils and 12.8g MDI are added, is stirred 4 minutes, quick stirring is lower to add 1.5g second two
Amine, is stirred 4 minutes, is added 0.8g ethylenediamines again under quick stirring, is stirred 4 minutes, add 6.9g octadecylamines, stirs 4 minutes,
The mol ratio of added MDI, ethylenediamine, ethylenediamine and octadecylamine is 4 successively:2:1:2,120 DEG C of constant temperature 20 minutes, then heats up
To 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to
110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 2
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：ZrOCl2·8H2O（22.5g）；NaOH（6g）；Ethanol zirconium（19g）；Ca(OH)2（2.6g）；12- hydroxyls
Base stearic acid（50g）；Decanedioic acid（18g）；Octadecylamine（6.9g）；Ethylenediamine（2.3g）；MDI（12.8g）；HVI500SN lubricates base
Plinth oil（100 DEG C of kinematic viscosity are 10mm2/ s, 400g）.
By 22.5gZrOCl2·8H2O is dissolved in 140g water, and 80g is contained to the 6g NaOH aqueous solution, is slowly added into above-mentioned
ZrOCl2The aqueous solution in, quick stirring obtains white precipitate, is filtrated to get precipitation, precipitation is washed rear standby with massive laundering.
150g HVI500SN lubricating base oils, 50g12- hydroxy stearic acids and 18g decanedioic acid are added into normal oleosterin kettle
In, stirring is heated to 90 DEG C, by 19g ethanol zirconium, the precipitation of above-mentioned brand-new and 2.6gCa (OH)2It is added thereto, calcium and zirconium rub
You are than being 1：4, in terms of zirconium, the precipitation of brand-new and the mol ratio of ethanol zirconium are 1：1, it is warming up to 105 DEG C of draining saponification.
50gHVI500SN lubrication bases are added in another is with heating, stirring, circulation, the normal-pressure reaction kettle of cooling
Oil and 12.8g MDI, are warming up to 120 DEG C, stir 4 minutes, and quick stirring is lower to add 1.5g ethylenediamines, stirs 4 minutes, quickly stirs
Mix down and add 0.8g ethylenediamines again, stir 4 minutes, add 6.9g octadecylamines, stir 4 minutes, added MDI, second two successively
The mol ratio of amine, ethylenediamine and octadecylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight polyureas.
The polyureas of gained eight is all squeezed into a upper kettle, stirred, 200 DEG C of constant temperature is finally warming up to 10 minutes.So
Afterwards, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing,
Degassing obtains finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
The eight polyureas molecular structural formulas contained in component are：
Embodiment 3
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Ca(OH)2（5.8g）；Zirconium-n-propylate（31.7g）；Zr(OH)4（3.1g）；Stearic acid（61.1g）；Nonyl
Diacid（16.2g）；Octadecylamine（6.9g）；Ethylenediamine（2.3g）；MDI（12.8g）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100
DEG C kinematic viscosity is 10mm2/ s, 1100g）.
400g full synthetic oils poly ＆ Alpha ,-olefin oil PAO10,61.1g stearic acid and 16.2g azelaic acids are added into normal oleosterin kettle
In, stirring is heated to 60 DEG C, by 31.7g zirconium-n-propylates, 5.8g Ca (OH)2With 3.1g Zr (OH)4It is added thereto, calcium and zirconium
Mol ratio is 1：1.5, in terms of zirconium, Zr (OH)4Mol ratio with zirconium-n-propylate is 1：5, it is warming up to 120 DEG C of draining saponification；Add
200g full synthetic oil poly ＆ Alpha ,-olefin oil PAO10 and 12.8g MDI, are stirred 8 minutes, and quick stirring is lower to add 1.5g ethylenediamines, stirs
Mix 8 minutes, add 0.8g ethylenediamines again under quick stirring, stir 8 minutes, addition 6.9g octadecylamines, stirring 8 minutes, successively
Added MDI, ethylenediamine, the mol ratio of ethylenediamine and octadecylamine are 4:2:1:2,100 DEG C of constant temperature 10 minutes, is finally warming 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, circulation
Filtering, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium base thickening agent 7.8
Measure %, the weight % of eight polyureas 1.8；The weight % of lubricating base oil 90.4.
Embodiment 4
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Ca(OH)2（16.8g）；ZrO(OH)2（10.7g）；Ethanol zirconium（20.6g）；Stearic acid（107.8g）；
Decanedioic acid（38.3g）；Lauryl amine（5.2g）；Ethylenediamine（2.6g）；MDI（14.2g）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO6（100
DEG C kinematic viscosity is 5.8mm2/ s, 500g）；It is right, right '-di-iso-octyldiphenylamine（2g）.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, with ZrO (OH)2Instead of brand-new
Precipitation, 12- hydroxy stearic acids are replaced with stearic acid, octadecylamine is replaced with lauryl amine, with full synthetic oil poly ＆ Alpha ,-olefin oil PAO6 generations
For HVI500SN lubricating base oils, the ratio be the same as Example 1 of lubricating base oil used in three times, and treat that temperature is cooled to 110 DEG C,
2g pair is added, right '-di-iso-octyldiphenylamine is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；Each original
As above, assay is shown in Table 1 to the consumption of material.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium base thickening agent 24.5
Measure %；The weight % of eight polyureas 3.2；The weight % of lubricating base oil 72.0；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.3.Wherein, calcium
Mol ratio with zirconium is 1：0.67.
Embodiment 5
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Ca(OH)2（1.6g）；Zr(OH)4（0.5g）；Ethanol zirconium（0.8g）；12- hydroxy stearic acids（1.8g）；
Decanedioic acid（4.9g）；Octadecylamine（11.4g）；Para-totuidine（4.5g）；1,6- hexamethylene diamines（14.7g）；TDI（29.4g）；
HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 10mm2/ s, 160g）.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, with Zr (OH)4Instead of brand-new
Precipitation, when adding octadecylamine, is additionally added para-totuidine, ethylenediamine is replaced with 1,6- hexamethylene diamines, MDI is replaced with TDI, used in three times
The ratio be the same as Example 1 of lubricating base oil, as above, assay is shown in Table 1 to the consumption of each raw material.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium base thickening agent 3.6
Measure %, the weight % of eight polyureas 26.3；The weight % of lubricating base oil 70.1.Wherein, the mol ratio of calcium and zirconium is 1：0.25.
Embodiment 6
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Ca(OH)2（1g）；ZrO(OH)2（1.0g）；Ethanol zirconium（1.8g）；12- hydroxy stearic acids（2.7g）；
Acetic acid（2.7g）；Octadecylamine（5.7g）；1,6- hexamethylene diamines（3.7g）；TDI（7.4g）；HVI500SN lubricating base oils（100 DEG C of fortune
Kinetic viscosity is 10mm2/ s, 100g）.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, with ZrO (OH)2Instead of brand-new
Precipitation, replaces decanedioic acid with acetic acid, ethylenediamine is replaced with 1,6- hexamethylene diamines, MDI, lubricating base oil used in three times are replaced with TDI
Ratio be the same as Example 1, as above, assay is shown in Table 1 to the consumption of each raw material.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Constitute and be：Zirconium calcium base thickening agent
6.5 weight %, the weight % of eight polyureas 5.3；The weight % of lubricating base oil 88.2.Wherein, the mol ratio of calcium and zirconium is 1:1.
Embodiment 7
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Ca(OH)2（0.68g）；Zr(OH)4（0.73g）；Ethanol zirconium（1.23g）；12- hydroxy stearic acids
（2.7g）；Boric acid（1.7g）；Octadecylamine（5.7g）；1,6- hexamethylene diamines（3.7g）；TDI（7.4g）；Full synthetic oil poly ＆ Alpha ,-olefin oil
PAO40（100 DEG C of kinematic viscosity are 40mm2/ s, 160g）.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, with Zr (OH)4Instead of brand-new
Precipitation, replaces decanedioic acid with boric acid, replaces ethylenediamine with 1,6- hexamethylene diamines, MDI is replaced with TDI, use full synthetic oil poly alpha olefin
Oily PAO40 replaces HVI500SN lubricating base oils, the ratio be the same as Example 1 of lubricating base oil used in three times, the consumption of each raw material
As above, assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium base thickening agent 3.1
Measure %, the weight % of eight polyureas 4.0；The weight % of lubricating base oil 92.9.Wherein, the mol ratio of calcium and zirconium is 1:1.
Embodiment 8
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, at Ca (OH)2, brand-new precipitation and
The gross weight of ethanol zirconium is constant, in the case that the mol ratio of calcium and zirconium is constant, and the mol ratio of adjustment brand-new precipitation and ethanol zirconium is
1：0.1.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 9
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, at Ca (OH)2, brand-new precipitation and
The gross weight of ethanol zirconium is constant, in the case that the mol ratio of calcium and zirconium is constant, and the mol ratio of adjustment brand-new precipitation and ethanol zirconium is
1：10.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 10
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, in calcium and total consumption of zirconium raw material
It is constant, in the case that the mol ratio of calcium and zirconium is constant, ethanol zirconium is replaced with to the precipitation of brand-new.Each physicochemical property of gained fat
It is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 11
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, unlike, in calcium and total consumption of zirconium raw material
It is constant, in the case that the mol ratio of calcium and zirconium is constant, the precipitation of brand-new is replaced with into ethanol zirconium.Each physicochemical property of gained fat is shown in
Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of zirconium calcium soap thickening agent 16.7
Measure %, the weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 12
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, keeps rubbing for 12- hydroxy stearic acids and decanedioic acid
Your ratio, the precipitation of brand-new and ethanol zirconium mol ratio it is constant, unlike, the mol ratio for adjusting calcium and zirconium is 1：0.1, each consumption
It is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of calcium zirconium base thickening agent 16.7
Measure %；The weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Embodiment 13
The present embodiment is used for the calcium zirconium base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares calcium zirconium base octa-polyurea lubricating grease, keeps rubbing for 12- hydroxy stearic acids and decanedioic acid
Your ratio, the precipitation of brand-new and ethanol zirconium mol ratio it is constant, unlike, the mol ratio for adjusting calcium and zirconium is 1：10, each consumption
It is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：The weight of calcium zirconium base thickening agent 16.7
Measure %；The weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Comparative example 1
Zirconium base octa-polyurea lubricating grease is prepared according to the method for embodiment 1, mole of 12- hydroxy stearic acids and decanedioic acid is kept
Mol ratio than, the precipitation of brand-new and ethanol zirconium is constant, unlike, by Ca (OH)2The precipitation and ethanol zirconium of brand-new are replaced with,
Each consumption is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight % of zirconium base thickening agent 16.7；
The weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Comparative example 2
Method according to embodiment 1 prepares calcium base octa-polyurea lubricating grease, keeps mole of 12- hydroxy stearic acids and decanedioic acid
Than constant, unlike, the precipitation of brand-new and ethanol zirconium are replaced with into Ca (OH)2, each consumption be adjusted accordingly with keep thickening
Agent proportion is constant.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight % of calcium base thickening agent 16.7；
The weight % of eight polyureas 4.3；The weight % of lubricating base oil 79.0.
Each lubricating grease properties of sample data of table 1
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Stencil oil-dividing：SH/
T0324；Tetra-ball machine test（PB、PD）：SH/T0202；Tetra-ball machine test（D40 60）：SH/T0204；Ball bearing lubricating life：ASTM
D3336。
Table 1（It is continuous）Each lubricating grease properties of sample data
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Stencil oil-dividing：SH/
T0324；Tetra-ball machine test（PB、PD）：SH/T0202；Tetra-ball machine test（D40 60）：SH/T0204；Ball bearing lubricating life：ASTM
D3336。
Embodiment 1 is compared with comparative example 1 and comparative example 2 respectively as can be seen that the polyureas of calcium zirconium base eight of the present invention
The dropping point of lubricating grease is far above zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, and extension work cone penetration enters with Drawing cone
The difference of degree is much smaller than zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, and water drenches number of dropouts and moistened much smaller than the polyureas of zirconium base eight
Consistent lubricant and calcium base octa-polyurea lubricating grease, salt spray test are better than zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, steel mesh point
Oil value is much smaller than zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, tetra-ball machine test PB、PDValue is more than the polyureas of zirconium base eight profit
Consistent lubricant and calcium base octa-polyurea lubricating grease, tetra-ball machine test D40 60Value lubricates less than zirconium base octa-polyurea lubricating grease and the polyureas of calcium base eight
Fat, ball bearing lubricating life is more than zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, illustrates the calcium zirconium base eight of the present invention
Heat-resisting quantity, mechanical stability, water-resistance and the adhesiveness of polyurea grease, resistance to saltfog, colloid stability, extreme pressure anti-wear
Zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease are superior to lubricating life.
Embodiment 1 and embodiment 2 are compared as can be seen that calcium zirconium base six polyurea grease in situ prepared, has
More preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, with longer profit
The sliding life-span；Embodiment 1 is compared to oxide and/or hydroxide as can be seen that zirconium with embodiment 8 and embodiment 9 respectively
The mol ratio of thing and zirconium alkoxide is 1：0.5-5, the calcium zirconium base octa-polyurea lubricating grease of preparation, with more preferable heat-resisting quantity, machine
Tool stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, with longer lubricating life；By 1 point of embodiment
It is not compared with embodiment 10 and embodiment 11 as can be seen that the raw material for preparing the zirconium of calcium zirconium base thickening agent is the oxide of zirconium
And/or the mixture of hydroxide and zirconium alkoxide, the calcium zirconium base octa-polyurea lubricating grease of preparation, with more preferable heat-resisting quantity,
Mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, with longer lubricating life；By embodiment 1
It is compared respectively with embodiment 12 and embodiment 13 as can be seen that the mol ratio of calcium and zirconium is 1：0.25-4, the calcium zirconium of preparation
Base octa-polyurea lubricating grease, with more preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure
Wear resistence, with longer lubricating life.
The calcium zirconium base octa-polyurea lubricating grease of the present invention, compared to zirconium base octa-polyurea lubricating grease and calcium base octa-polyurea lubricating grease, tool
There are more preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear,
With longer lubricating life, especially when the mol ratio of calcium in lubricating grease and zirconium is 1：0.25-4；Prepare calcium zirconium base thickening agent
The raw material of zirconium is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide；In terms of zirconium, the oxide and/or hydrogen of zirconium
The mol ratio of oxide and zirconium alkoxide is 1：During 0.5-5, the heat-resisting quantity of calcium zirconium base octa-polyurea lubricating grease, mechanical stability,
Water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear and lubricating life can be greatly improved.The lubricating grease of the present invention
Preparation technology is simple, cost is low, product quality is stable.The lubricating grease of the present invention can be widely used for high speed, heavy load operating, oil
The bearing lubrication such as field drilling well.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (28)
1. a kind of calcium zirconium base octa-polyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, including following components：1-59
Weight % calcium zirconium base thickening agent；1-59 weight % polyurea compound；40-95 weight % base oil, wherein, the calcium zirconium
Base thickening agent be by component A, component B and component C react generation calcium zirconium soap, wherein, the component A be higher fatty acids with it is low
The mixture of level straight chain fatty acid, the component B is the oxide and/or hydroxide of calcium, and the component C is the oxidation of zirconium
At least one of thing, the hydroxide of zirconium and zirconium alkoxide, the polyurea compound are eight polyurea compounds, wherein, it is described
In calcium zirconium base thickening agent, the mol ratio of calcium and zirconium is 1：0.1-10, the higher fatty acids is the straight chain fatty that carbon number is 8-24
Acid or hydroxy fatty acid, the lower straight aliphatic acid are selected from ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptan two
At least one of acid, suberic acid, azelaic acid, decanedioic acid and dodecanedioic acid.
2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：3-40 weights
Measure % calcium zirconium base thickening agent；2-40 weight % eight polyurea compounds；50-93 weight % base oil.
3. lubricating grease according to claim 1, wherein, in the calcium zirconium base thickening agent, the mol ratio of calcium and zirconium is 1：
0.25-4。
4. lubricating grease according to claim 1 or 2, wherein, the component C for zirconium oxide and/or hydroxide with
The mixture of zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10.
5. lubricating grease according to claim 4, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be 1：0.5-5.
6. lubricating grease according to claim 1, wherein, the higher fatty acids is selected from laurate, oleic acid, palmitic acid, hard
At least one of resin acid, 12- hydroxy stearic acids, eicosyl carboxylic acid.
7. lubricating grease according to claim 1 or 2, wherein, the mol ratio of higher fatty acids and lower straight aliphatic acid is
1：0.2-10.
8. lubricating grease according to claim 1 or 2, wherein, the oxide and/or hydroxide of zirconium are selected from ZrO2、ZrO
(OH)2、Zr(OH)4At least one of and their hydrate.
9. lubricating grease according to claim 1 or 2, wherein, the formula of the zirconium alkoxide is Zr (OR1)4, R1For C1-
C10 alkyl.
10. lubricating grease according to claim 9, wherein, the zirconium alkoxide is selected from ethanol zirconium, zirconium-n-propylate, n-butanol
At least one of zirconium, zirconium tert-butoxide and n-amyl alcohol zirconium.
11. lubricating grease according to claim 1 or 2, wherein, eight polyurea compound has following structure：
Wherein, R1It is alkyl, cycloalkyl or aryl, R2It is alkylidene or arlydene, R3It is arlydene, alkylidene or cycloalkylidene.
12. lubricating grease according to claim 11, wherein, R1It is phenyl or substituted phenyl, or the alkyl that carbon number is 8-24
Or cycloalkyl；R2It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R3It is arlydene, alkylene that carbon number is 6-30
Base or cycloalkylidene.
13. lubricating grease according to claim 12, wherein, R1It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon
Number is 10-18 alkyl or cycloalkyl, R2It is phenylene or biphenylene, or the alkylidene that carbon number is 2-8；R3It is selected from -(CH2）6At least one of-.
14. lubricating grease according to claim 1 or 2, wherein, the base oil is selected from mineral oil, artificial oil and vegetable oil
At least one of, described 100 DEG C of kinematic viscosity of base oil are 2-150mm2/s。
15. the preparation method of the calcium zirconium base octa-polyurea lubricating grease in claim 1-14 described in any one, it is characterised in that should
Method includes：Calcium zirconium base thickening agent, eight polyurea compounds and part basis oil is well mixed, in 180-230 DEG C of constant temperature refining,
Surplus base oil is added, necessary additive is added, obtains finished product.
16. the preparation method of the calcium zirconium base octa-polyurea lubricating grease in claim 1-14 described in any one, it is characterised in that should
Method includes：
(1) component A, component B and component C are mixed in base oil, heat up draining saponification, wherein, the component A is senior fat
The mixture of fat acid and lower straight aliphatic acid, the component B is the oxide and/or hydroxide of calcium, and the component C is zirconium
At least one of oxide, the hydroxide of zirconium and zirconium alkoxide, the mol ratio of calcium and zirconium is 1：0.1-10；
(2) base oil and diisocyanate are added in mixture obtained by step (1), diamines, diamines and list is then sequentially added
Amine is reacted；
(3) mixture obtained by step (2) is warming up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary addition
Agent, obtains finished product.
17. method according to claim 16, wherein, in step (1), the mol ratio of calcium and zirconium is 1：0.25-4.
18. the method according to claim 16 or 17, wherein, in step (1), the component A and base oil are mixed and added
Heat arrives 60-90 DEG C, adds component B and component C, in 90-120 DEG C of draining saponification, wherein, component C is the oxide and/or hydrogen of zirconium
The mixture of oxide and zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：
0.1-10。
19. method according to claim 18, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be 1：0.5-5.
20. the method according to claim 16 or 17, wherein, the mol ratio of higher fatty acids and lower straight aliphatic acid is
1：0.2-10.
21. the method according to claim 16 or 17, wherein, in step (2), added in mixture obtained by step (1)
Base oil and diisocyanate, add diamines, stir 2-8 minutes, and diamines is added again, stir 2-8 minutes, add monoamine,
The mol ratio for stirring the diisocyanate added by 2-8 minutes, each time, diamines, diamines and monoamine is 4:2:1:2.
22. the method according to claim 16 or 17, wherein, in step (3), first in 100-120 DEG C of 10-20 points of constant temperature
Clock, is finally warming up to 180-230 DEG C of constant temperature 5-20 minutes；Base oil is added, treats that temperature is cooled to 80-130 DEG C, adds necessary
Additive, stirring, circulating filtration, homogenizing, degassing.
23. the method according to claim 16 or 17, wherein, the structural formula of the monoamine is R1-NH2、R1’-NH2, wherein,
R1、R1’It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
24. method according to claim 23, wherein, the monoamine be selected from aniline, m-chloroaniline, parachloroanilinum and/
Or the arylamine of para-totuidine, and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
25. the method according to claim 16 or 17, wherein, the structural formula of the diamines is NH2-R2-NH2, wherein, R2It is
Carbon number is 2-8 alkylidene, or phenylene or biphenylene.
26. method according to claim 25, wherein, the diamines is to be selected from p-phenylenediamine, o-phenylenediamine, 4,4- biphenyl
The aromatic amine of diamines and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.
27. the method according to claim 16 or 17, wherein, the structure of the diisocyanate is OCN-R3- NCO, R3It is
Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.
28. method according to claim 27, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), methyl two
Phenyl diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and the isocyanide of an xyxylene two
At least one of acid esters.
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| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN103031182A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Composite zirconium-based octaurea lubrication grease and its preparation method |
| CN103060068A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN103031182A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Composite zirconium-based octaurea lubrication grease and its preparation method |
| CN103060068A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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