CN105586130B - Excellent urea-based lubricating grease composition of a kind of antioxygen property and preparation method thereof - Google Patents
Excellent urea-based lubricating grease composition of a kind of antioxygen property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the urea-based lubricating grease composition that a kind of antioxygen property is excellent, and on the basis of the weight of lubricant composition, the lubricant composition includes following components：The additive of 65 95 weight % lubricating base oil, 4 30 weight % carbamido thickening agent and 0.1 15 weight %, the additive contain the compound of structure shown in formula (I).Present invention also offers the preparation method of the excellent urea-based lubricating grease composition of antioxygen property.The urea-based lubricating grease composition of the present invention, due to containing antioxidant, drastically increases the antioxidant capacity of lubricating grease.The lubricating grease of the present invention has splendid heat resistance, mechanical stability, inoxidizability, colloid stability and water proofing property etc., can be competent in the harsh working conditions such as high temperature, high speed, high load capacity, more water.
Description
Technical field
The present invention relates to lubricating grease field, in particular it relates to the urea that a kind of antioxygen property containing special additive is excellent
Base grease composition and preparation method thereof.
Background technology
Urea-base grease is to be thickened mineral oil or artificial oil by organic compound urea and obtained, thickening agent not metal ion,
The catalytic action that metal ion aoxidizes to base oil is avoided, urea-base grease has good oxidation stability, thermostability
And other various premium properties, also there is especially long service life, be a kind of multipurpose grease, various lubricating grease can be prepared
Meet different requirements, suitable for high temperature, low temperature, high load capacity, wide velocity interval and the occasion contacted with impedance dielectric, extensively
It is general to be applied to the industries such as electrical equipment, metallurgy, food, automobile, papermaking.
Urea-base grease typically makees base oil from mineral oil or artificial oil, but mineral oil can biology in natural environment
Degradation capability is poor, gathers in the environment and environment is polluted.Therefore the demand of Green Lubricants is in ascendant trend year by year,
Green Lubricants typically have polyethers, synthetic ester and crude vegetal.Wherein vegetable oil cost is cheap, abundance, have it is excellent
Greasy property, viscosity index (VI) is high, biological degradability is good, but contain substantial amounts of double bond in general vegetable oil molecule, and oxidation is stabilized
Property is poor.CN101407746A mixes alcohol, metatitanic acid, four butyl esters and vegetable oil, is reacted at a temperature of 20-80 DEG C, and reaction finishes point
From remaining alcohol, that is, modified vegetable oil is obtained, substantially increase oxidation stability, the extreme pressure anti-wear of vegetable oil.
Have the performance that a large amount of patents inquire into urea-base greases in recent years, such as US5158694 by diisocyanate and water and
Amine reaction prepares polyurea grease, but the dropping point of its product is between 230-260 DEG C；Presence of the CN1272530 in base oil
Under, make C8-C24 fatty amines and excessive di-isocyanate reaction, unreacted diisocyanate is neutralized with water, continues to react
It it is 130-200 DEG C to temperature, two urea grease dropping points prepared by this method reach 260-330 DEG C；CN1580211 is by organic amine and different
Cyanate is mixed and reacted, and after temperature of charge is increased to 100-150 DEG C, adding quench oil makes material cool down rapidly, is ground into
Fat, urea-base grease prepared by this method have stable vibration values；CN1408825 50-120 DEG C by base oil, alkylamine and
Excessive diisocyanate mixing, is reacted, and is added in excessive water with unreacted diisocyanate, is warming up to melting, adds
Enter quench oil, cool down out kettle and obtain the lubricating grease of appearance transparent；CN101368129 adds the extreme pressure of borate into system
Antiwear additive, the combination property of lubricating grease is improved, reduces cost；CN1657599 in polyurea grease by adding calcic
Compound improves the oxidation stability of lubricating grease, its complex process；CN101111591A is related to four urea greases, but prepares
Technics comparing is complicated, and also introduces metal ion, and this will influence the oxidation stability of polyurea grease；CN101693851A
Using two ureas, triuret, four ureas mixture and introduce fat made from amidic-salt thickening agent, have excellent high-temperature behavior, anti-current
The property lost, good extreme pressure anti-wear；Thickening agent used in CN1056313 is two ureas and four urea mixtures, and the fat is operating for a long time
Excellent performance is had more in machinery.
The life-span of lubricating grease can shorten with temperature in use rising or the extension of lubrication time.Chemically say, make in nature
Metal soap for thickening agent is the major reason for causing lubricating grease oxidation deterioration.In order to suppress the oxidation deterioration of lubricating grease, prevent
Oxidation product causes the corrosion of metal surface, to add appropriate antioxidant additive.At present, conventional antioxidant mainly divides
For amine and the class of phenols two.Phenolic antioxidant generally comprises BHT, 2,6- di-tert-butylphenols etc., but it makes
It is relatively low with temperature, typically within 150 DEG C.Amine antioxidants are mainly alkylated diphenylamine, or the phenyl-naphthylamines of alkylation
Deng.
The content of the invention
The invention aims to meet the high request to the antioxygen property of lubricating grease, there is provided a kind of antioxygen property is excellent
Urea-based lubricating grease composition and preparation method thereof.
The present inventor has found that the additive in lubricant composition contains structure shown in formula (I) under study for action
Antioxidant：
It can make lubricant composition that there is excellent antioxygen property.
Therefore, to achieve these goals, on the one hand, the invention provides the urea-base grease that a kind of antioxygen property is excellent
Composition, on the basis of the weight of lubricant composition, the lubricant composition includes following components：65-95 weight %'s
The additive of lubricating base oil, 4-30 weight % carbamido thickening agent and 0.1-15 weight %, the additive contain formula (I) institute
Show the compound of structure：
Preferably, on the basis of the weight of lubricant composition, the lubricant composition includes following components：70-90
The additive of weight % lubricating base oil, 4-28 weight % carbamido thickening agent and 1-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the content of the compound of structure shown in formula (I) is 0.1-3
Weight %, more preferably 0.2-1 weight %.
On the other hand, the invention provides a kind of preparation method of the excellent urea-based lubricating grease composition of antioxygen property, institute
The method of stating includes：
(1) partial lubrication base oil, diisocyanate, amine hybrid reaction are generated into carbamido thickening agent；
(2) step (1) is reacted into gained system and is warming up to 180-210 DEG C, keep 5-25min, add remaining lubrication base
Plinth oil, stirring are cooled to 90-130 DEG C, add additive, are well mixed；
(3) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, different by two
The dosage of carbamido thickening agent prepared by cyanate, amine is 4-30 weight %, and the dosage of additive is 0.1-15 weight %, described to add
Agent is added to contain the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-90 weight %, by two
The dosage of carbamido thickening agent prepared by isocyanates, amine is 4-28 weight %, and the dosage of additive is 1-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the dosage of the compound of structure shown in formula (I) is 0.1-3
Weight %, more preferably 0.2-1 weight %.
The urea-based lubricating grease composition of the present invention, due to containing antioxidant, drastically increases the antioxidant capacity of lubricating grease.
The lubricating grease of the present invention has splendid heat resistance, mechanical stability, inoxidizability, colloid stability and water proofing property etc., can
It is competent in the harsh working conditions such as high temperature, high speed, high load capacity, more water.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing antioxidant.
Fig. 2 is the reaction equation of (b) the step of preparing antioxidant.
Fig. 3 is the reaction equation of (c) the step of preparing antioxidant.
Fig. 4 is the hydrogen spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 5 is the carbon spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 6 is the mass spectrogram of antioxidant prepared by preparation example.
Embodiment
The embodiment of the present invention is described in detail below.It is 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 the urea-based lubricating grease composition that a kind of antioxygen property is excellent, using the weight of lubricant composition as
Benchmark, lubricant composition include following components：65-95 weight % lubricating base oil, 4-30 weight % carbamido thickening agent
With 0.1-15 weight % additive, additive contains the compound of structure shown in formula (I)：
In the present invention, what antioxidant referred to is the compound of structure shown in formula (I).
In the present invention, it is preferable that on the basis of the weight of lubricant composition, the lubricant composition is included with the following group
Point：The additive of 70-90 weight % lubricating base oil, 4-28 weight % carbamido thickening agent and 1-10 weight %.
In the present invention, on the basis of the weight of lubricant composition, the content of the compound of structure is preferably shown in formula (I)
0.1-3 weight %, more preferably 0.2-1 weight %.
It is contemplated that the compound of structure shown in formula (I) is contained and reality by the additive in urea-based lubricating grease composition
Existing goal of the invention, even if urea-based lubricating grease composition has the performances such as excellent antioxygen.Therefore, for each normal in urea-base grease
The selection of component is advised, is not limited specifically.
In the present invention, lubricating base oil can be lubricating base oil commonly used in the art, for example, can be mineral oil,
At least one of vegetable oil and artificial oil.100 DEG C of kinematic viscosity of lubricating base oil are preferably 5-50mm2/ s, more preferably 5-
32mm2/s.For the specific species of mineral oil, vegetable oil and artificial oil, also there is no particular limitation, and this area can be used normal
Mineral oil, vegetable oil and artificial oil, for example, mineral oil can select paraffinic base, cycloalkyl series, vegetable oil can be castor
At least one of sesame oil, rapeseed oil, peanut oil and soybean oil etc., artificial oil can be poly-a-olefin oil (PAO), Esters oil, fluorine
At least one of oil and silicone oil etc..
In the present invention, carbamido thickening agent is preferably the reaction product of amine and diisocyanate, for example, carbamido thickening agent can be with
For at least one of two carbamido thickening agents, four carbamido thickening agents, six carbamido thickening agents and eight carbamido thickening agents.
The structure of two carbamido thickening agents is preferably：
The structure of four carbamido thickening agents is preferably：
The structure of six carbamido thickening agents is preferably：
The structure of eight carbamido thickening agents is preferably：
Above-mentioned two, four, six, in the structural formulas of eight carbamido thickening agents, R1、R1’It can be the same or different, Ke Yishi
Alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, and aryl can be phenyl or substitution
Phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution phenyl.
Wherein, R2Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be with
It is phenylene or biphenylene.
Wherein, R3Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can
Think 6-30, preferably 6-20, R3 is more preferably In
It is at least one.
Above-mentioned carbamido thickening agent can use the thinkable various methods of those skilled in the art institute to obtain.
In the present invention, because the antioxidant of structure shown in formula (I) and other additives have preferable compatibility, therefore,
According to the use needs of lubricating grease, additive of the invention can also contain extreme pressure anti-wear additives.
In the present invention, for extreme pressure anti-wear additives species and content without particular/special requirement, the conventional kind in this area can be used
Class and content.For example, extreme pressure anti-wear additives can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two sulphur
For dialkyl amido lead formate, molybdenum disulfide, polytetrafluoroethylene (PTFE), dibutyl dithiocaarbamate antimony, tungsten disulfide, curing
At least one of selenium, fluorographite, calcium carbonate and zinc oxide, the content of extreme pressure anti-wear additives can account for lubricant composition gross weight
The 0.5-12 weight % of amount, preferably 0.5-5 weight %.
In the present invention, the preparation method of the compound of structure preferably includes shown in formula (I)：
(a) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II),
(b) the intermediate M that step (a) obtains is contacted with bromide reagent and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product that step (b) obtains is contacted with the compound shown in formula (IV) and carry out coupling reaction, production
(I) antioxidant shown in,
In step (a) of the present invention, the condition of condensation reaction preferably includes：Under an inert atmosphere, in the first solvent,
In the presence of one catalyst, 15- is risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted into 0.5-1.5h at -20-0 DEG C
30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, such as can be by gases such as nitrogen, argon gas
There is provided.
It will be understood by those skilled in the art that in order that stable reaction progress, reacts 0.5-1.5h at -20-0 DEG C
After rise to 15-30 DEG C, it should be to slowly warm up to 15-30 DEG C, for example, can by -20-0 DEG C react 0.5-1.5h after body
System is placed under 15-30 DEG C of environment temperature, reaction system itself is to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethanol, DMF and acetonitrile
Kind, more preferably methanol and/or acetonitrile, are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, p-methylbenzoic acid and benzene
At least one of sulfonic acid, more preferably acetic acid.
In the present invention, the dosage of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but formaldehyde and benzene can
With appropriate excessive.The mol ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably 0.9-1.5:0.9-10:0.9-10.
In step (a) of the present invention, the dosage of the first catalyst can be catalytic amount, with mole of 2,6- DI-tert-butylphenol compounds
On the basis of number, the dosage of the first catalyst is preferably 5-100 moles of %, more preferably 10-30 moles of %.
It will be understood by those skilled in the art that in step (a) of the present invention, in order to obtain purer intermediate M, also
Needing to post-process reacted system, the mode of post processing can include removal of solvent under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, reacted system is removed into solvent at 0.01-0.05MPa, 40-60 DEG C,
It is subsequently poured into the ethyl acetate (or dichloromethane) of 1-10 times of volume, respectively with distilled water and saturated common salt water washing, then
The drier such as anhydrous calcium chloride or anhydrous sodium sulfate is added at 15-30 DEG C, keeps 10-60min.It is filtered to remove drier
Afterwards, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction equation of condensation reaction as schemed
Shown in 1, in Fig. 1, the first solvent is using methanol, and the first catalyst is using acetic acid, purpose by way of example only, no
The scope of the present invention is construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction preferably includes：Under an inert atmosphere, in the second solvent,
In the presence of two catalyst, under the conditions of lucifuge, intermediate M that step (a) obtains is reacted at 15-30 DEG C with bromide reagent
1-2h, then it is quenched with quencher.
" inert atmosphere " is as it was previously stated, will not be repeated here.
It will be understood by those skilled in the art that more stably being carried out to react, slowly add preferably into intermediate M
Enter brominated reagent.
In the present invention, the second solvent is preferably selected from least one of tetrahydrofuran, dichloromethane, chloroform and ether, more
Preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azodiisobutyronitrile
At least one of (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more preferably NBS.
In step (b) of the present invention, it is quenched with quencher, quencher can be quencher commonly used in the art, such as
It can be saturated aqueous common salt.
In step (b) of the present invention, the dosage of intermediate M and bromide reagent is substantially equimolar amounts, but bromide reagent one
As can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate.Intermediate M and bromide reagent mol ratio are preferably 0.9-
1.2:0.9-3.0。
In step (b) of the present invention, the dosage of the second catalyst can be catalytic amount, on the basis of intermediate M molal quantity,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the inventive method step (b), intermediate M contacts the reaction equation for carrying out bromo-reaction with bromide reagent as schemed
Shown in 2, in Fig. 2, bromide reagent purpose by way of example only, is not construed as limiting using NBS to the scope of the present invention.
In step (b) of the present invention, in addition to the bromination product shown in generation formula (III), the bromo production at also micro ortho position
Thing generates, and is generated without the bromination product of meta, but the amount of the bromination product at ortho position very pettiness, does not have substantive shadow to subsequent reactions
Ring, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, in order to obtain purer bromination product,
Also need to post-process the system after being quenched, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, example
Such as, the system distillation water washing after being quenched, it is dry then to add anhydrous calcium chloride or anhydrous sodium sulfate etc. at 15-30 DEG C
Drying prescription, keep 10-60min.After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromine
For product.
In step (c) of the present invention, the condition of coupling reaction preferably includes：Under an inert atmosphere, in the 3rd solvent,
In the presence of three catalyst, the bromination product that step (b) obtains and the compound shown in formula (IV) are reacted at 80-100 DEG C
4-8h。
" inert atmosphere " is as it was previously stated, will not be repeated here.
In the present invention, in order that stable reaction is carried out, 80-100 DEG C is preferably gradually heating to, it is then anti-at 80-100 DEG C
Answer 4-8h.
In the present invention, the 3rd solvent is preferably selected from least one of dichloromethane, chloroform, toluene and tetrahydrofuran, more
Preferably dichloromethane.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali.Palladium salt is preferably selected from palladium and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3]；Part is preferably selected from tri-tert phosphorus, dinaphthol (BINAP) and double (diphenylphosphines
At least one of base) ferrocene (dppf)；Alkali is preferably selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate extremely
Few one kind.
In step (c) of the present invention, the dosage for the compound shown in bromination product and formula (IV) that step (b) obtains is substantially
For equimolar amounts, but the compound shown in formula (IV) can be suitably excessive.Shown in the bromination product and formula (IV) that step (b) obtains
The mol ratio of compound be preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the dosage of catalyst can be catalytic amount, on the basis of the molal quantity of bromination product, palladium
The dosage of salt is preferably 5-50 moles of %, more preferably 5-20 moles of %, is still more preferably 5-10 moles of %；The use of part
Amount is preferably 5-50 moles of %, more preferably 10-30 moles of %；The dosage of alkali is preferably 5-50 moles of %, more preferably 10-30
Mole %.
In step (c) of the present invention, bromination product that step (b) obtains contacts with the compound shown in formula (IV) to be coupled
The reaction equation of reaction is as shown in figure 3, in Fig. 3, and palladium salt is using palladium, purpose by way of example only, not to this
The scope of invention is construed as limiting.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e. antioxygen shown in formula (I)
Agent, the inventive method preferably also include post-processing reacted system, and the mode of post processing can include filtering, solvent
Dilution, washing, dry, removal of solvent under reduced pressure, for example, the filtrate after reacted system is filtered pours into the second of 1-10 times of volume
In acetoacetic ester (or dichloromethane), then with distillation water washing, anhydrous calcium chloride or anhydrous sulphur are then added at 15-30 DEG C
The drier such as sour sodium, keep 10-60min.After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C,
To obtain the antioxidant shown in formula (I).
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention is preferably carried out under agitation, for
Mixing speed can be the conventional mixing speed in this area, for example, mixing speed can be 100-800rpm without particular/special requirement.
The present invention is prepared in the method for the compound of structure shown in formula (I), molten for the first solvent, the second solvent and the 3rd
The amount of agent can be the conventional solvent load in this area, this is known to those skilled in the art, herein no longer without particular/special requirement
Repeat.
As described above, it is contemplated that structure shown in formula (I) is contained by the additive in urea-based lubricating grease composition
Compound and realize goal of the invention, even if lubricant composition has the excellent performance such as anti-oxidant.Therefore, lubricated for urea groups
The preparation method of fat can use method commonly used in the art, for example, second aspect, the present invention also carries without particular/special requirement
A kind of preparation method of the excellent urea-based lubricating grease composition of antioxygen property is supplied, this method includes：
(1) partial lubrication base oil, diisocyanate, amine hybrid reaction are generated into carbamido thickening agent；
(2) step (1) is reacted into gained system and is warming up to 180-210 DEG C, keep 5-25min, add remaining lubrication base
Plinth oil, stirring are cooled to 90-130 DEG C, add additive, are well mixed；
(3) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, different by two
The dosage of carbamido thickening agent prepared by cyanate, amine is 4-30 weight %, and the dosage of additive is 0.1-15 weight %, additive
Compound containing structure shown in formula (I)：
It will be understood by those skilled in the art that in the inventive method, the dosage of lubricating base oil is partial lubrication base
The dosage and the dosage sum of remaining lubricating base oil of plinth oil.
In the inventive method, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-
90 weight %, the dosage of the carbamido thickening agent prepared by diisocyanate, amine are 4-28 weight %, and the dosage of additive is 1-10
Weight %.
In the inventive method, on the basis of the weight of lubricant composition, the dosage of the compound of structure is excellent shown in formula (I)
Elect 0.1-3 weight %, more preferably 0.2-1 weight % as.
It is for step (1), partial lubrication base oil, diisocyanate, amine hybrid reaction generation urea groups is thick in the present invention
The method of agent can use various methods commonly used in the art without particular/special requirement, such as：
When preparing two carbamido thickening agents, method can include：Monoamine and 1/5-2/5 base oil Hybrid Heating are arrived
50-80 DEG C, 2-8 minutes are stirred, organic amine is melted completely；Again by 1/5-2/5 base oil and diisocyanate Hybrid Heating
To 50-80 DEG C, 2-8 minutes are stirred, diisocyanate is melted completely；Then above-mentioned two groups of solution is mixed, at 80-100 DEG C,
React 20-60min.The mol ratio of diisocyanate and monoamine is 1:2.
When preparing four carbamido thickening agents, method can include：First 1/5-2/5 base oil is mixed with diisocyanate
50-60 DEG C is heated to, adds diamines, is warming up to 80-100 DEG C, reacts 20-60min；1/5-2/5 base oil is mixed with individual palpation
Conjunction is heated to 50-60 DEG C；Above two solution is mixed, at 80-100 DEG C, reacts 20-60min.Diisocyanate, diamines with
The mol ratio of monoamine is 2:1:2.
When preparing six carbamido thickening agents, method can include：First by 1/5-1/3 base oil and part diisocyanate
Hybrid Heating is to 50-70 DEG C；Again by 1/5-1/3 base oil and monoamine Hybrid Heating to 50-70 DEG C, it is slowly added into above-mentioned mixed
In compound, 80-100 DEG C is warming up to, reacts 20-60min, diamines is added thereto, 80-100 DEG C of constant temperature, reacts 20-60min；
1/5-1/3 base oil and remaining diisocyanate Hybrid Heating are slowly added into said mixture to 50-70 DEG C again
In, 80-100 DEG C of constant temperature, react 20-60min.Mole of added diisocyanate, monoamine, diamines and diisocyanate successively
Than for 2:2:2:1.
When preparing eight carbamido thickening agents, method can include：1/5-2/5 lubricating base oil is mixed with diisocyanate
Conjunction is heated to 50-70 DEG C, adds diamines, is warming up to 80-100 DEG C, reacts 20-60min, adds diamines, constant temperature 80-100 again
DEG C, react 20-60min；By 1/5-2/5 lubricating base oil and monoamine Hybrid Heating to 50-70 DEG C, said mixture is added to
In, 80-100 DEG C of constant temperature, react 20-60min.The mol ratio of added diisocyanate, diamines, diamines and monoamine is successively
4:2:1:2。
In the present invention, 1/5-2/5,1/5-1/3 lubricating base oil, which refer respectively to account for, prepares urea-based lubricating grease composition institute
With 1/5-2/5,1/5-1/3 of lubricating base oil total amount.
The inventive method is preferably carried out under agitation, for stirring speed without particular/special requirement, such as can be 20-
400rpm。
It will be understood by those skilled in the art that according to by diisocyanate, amine preparation carbamido thickening agent dosage,
The dosage of diisocyanate, amine counter can be released, this is known to those skilled in the art, will not be repeated here.
In the inventive method, diisocyanate structure is OCN-R3- NCO, R3Can be that carbon number is 6-30, preferably 6-20's
Arlydene, alkylidene or cycloalkylidene, more preferably Deng.
Preferable diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- it is sub- oneself
Group diisocyanate (HDI), in dicyclohexylmethyl diisocyanate (HMDI) and an xylylene diisocyanate (XDI) etc.
At least one.
Monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R1-NH2, wherein, R1Can 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 the phenyl of C1-C3 alkyl or halogen substitution.Preferable monoamine can be selected from aniline, m-chloroaniline, parachloroanilinum, right
The arylamine of toluidines, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine, cyclohexylamine fatty amine.
Diamines can be fatty amine or arylamine, structural formula NH2-R2-NH2, wherein, R2Can be alkylidene or arlydene,
The carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferably diamines can be
Selected from p-phenylenediamine, o-phenylenediamine, 4,4- benzidines aromatic amine, and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines
Straight-chain fatty amine.
Lubricating base oil, additive are as it was previously stated, will not be repeated here.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
The physico-chemical analysis method of product：Constituent content is determined by inductively coupled plasma ion emission spectroscopy method.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Extend work cone penetration：GB
2360-1980；Aoxidize initial temperature：ASTM D 5483；Stencil oil-dividing：SH/T0324；Anticorrosive property：GB/T 5018；Water drenches
Number of dropouts：SH/T 0109；Copper corrosion：GB/T 7326.
Preparation example
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Methanol and 0.01mol acetic acid, after sufficiently cool in ice-water bath, be then respectively adding 0.1mol 2,6- di-tert-butyls
Phenol, 0.2mol formaldehyde and 0.3mol benzene.Reaction removes ice-water bath after 1 hour, and 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Stream stops reaction after 2 hours, reacted system is steamed into solvent at 0.03MPa, 50 DEG C, then adds 250ml acetic acid second
Ester, and being transferred in separatory funnel, respectively with 100ml distilled water (twice) and 50ml saturated common salt water washings, and it is anhydrous to add 10g
Calcium chloride dries 20min at 25 DEG C, and the filtrate after filtering is evaporated off solvent under 40 DEG C, 0.03MPa, obtains midbody product
M1。
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Dry tetrahydrofuran, then dissolve in midbody product M1, and add 0.05mol ammonium nitrate, under the conditions of lucifuge slowly plus
Enter 0.1mol brominated reagents NBS.Stirring reaction 1.5h, is then quenched with saturated aqueous common salt at 25 DEG C, is then distilled with 100ml
Water (twice) washs, and adds 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Dichloromethane as solvent, be separately added into the benzotriazole compound of above-mentioned bromination product and 0.12mol, then add
0.02mol tri-tert phosphorus, 0.02mol sodium tert-butoxide and 0.005mol Pd (OAc)2.90 DEG C are gradually heating to, is continued
Stir 6h.Then the filtrate after reacted system is filtered adds 250ml ethyl acetate, and is transferred in separatory funnel, uses
100ml distilled water (twice) washs, and adds 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
S1 physico-chemical analysis data are as follows：Nitrogen content, 11.2%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 4, Fig. 5 and
Fig. 6.
Physico-chemical analysis data, Fig. 4, Fig. 5 and Fig. 6 from above-mentioned preparation example, which can be seen that S1, has knot shown in formula (I)
Structure.
Embodiment 1
The present embodiment is used to illustrate two urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) 62.07 grams of octadecylamines and 23.69 grams of para-totuidine are added to 262 grams of 500SN base oils (100 DEG C of viscosity is
10mm2/ s, similarly hereinafter) in, 60 DEG C are heated to, stirs 6 minutes, organic amine is melted completely；
(2) 40.02 grams of TDI are added in 252 grams of 500SN base oils, are heated to 60 DEG C, stirs 6 minutes, makes TDI complete
Melt；
(3) two groups of solution of step (1) and step (2) are mixed, at 90 DEG C, reacts 40min at 200 rpm；
(4) when being warming up to 180 DEG C, constant temperature refining 20min；
(5) 242 grams of 500SN base oils are added, stirring is cooled to 110 DEG C, adds 1.8 grams of S1,10.8 gram of two thio diformazan
Aminocarbamic acid molybdenum, stirs at 200 rpm；
(6) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.2 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of two carbamido thickening agent 14.1, the weight % of base oil 84.5.
Embodiment 2
The present embodiment is used to illustrate two urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) 54.74 grams of lauryl amines and 26.48 grams of para-totuidine are added to 262 grams of 150BS base oils (100 DEG C of viscosity is
31mm2/ s, similarly hereinafter) in, 50 DEG C are heated to, stirs 8 minutes, organic amine is melted completely；
(2) 44.72 grams of TDI are added in 252 grams of 150BS base oils, are heated to 50 DEG C, stirs 8 minutes, makes TDI complete
Melt；
(3) two groups of solution of step (1) and step (2) are mixed, at 80 DEG C, reacts 60min under 180rpm；
(4) when being warming up to 190 DEG C, constant temperature refining 15min；
(5) 242 grams of 150BS base oils are added, stirring is cooled to 90 DEG C, adds 9 grams of S1,10.8 grams of dithiodimethyl ammonia
Base formic acid molybdenum, stirs under 180rpm；
(6) 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S11 weight %, two thio diformazans
Aminocarbamic acid molybdenum 1.2 weight %, the weight % of two carbamido thickening agent 14, the weight % of base oil 83.8.
Embodiment 3
The present embodiment is used to illustrate two urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) 54.49 grams of octadecylamines and 20.86 grams of para-totuidine are added to 262 grams of PAO6 synthetic hydrocarbon oils (100 DEG C of viscosity
For 5.8mm2/ s, similarly hereinafter) in, 70 DEG C are heated to, stirs 4 minutes, organic amine is melted completely；
(2) 50.64 grams of MDI are added in 252 grams of PAO6 synthetic hydrocarbon oils, are heated to 70 DEG C, stirs 4 minutes, makes MDI complete
Melt；
(3) two groups of solution of step (1) and step (2) are mixed, at 100 DEG C, reacts 20min at 300 rpm；
(4) when being warming up to 200 DEG C, constant temperature refining 10min；
(5) 242 grams of PAO6 synthetic hydrocarbon oils are added, stirring is cooled to 120 DEG C, adds 3.6 grams of S1,10.8 gram of two thio diformazan
Aminocarbamic acid molybdenum, stirs at 300 rpm；
(6) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.4 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of two carbamido thickening agent 14.1, the weight % of base oil 84.3.
Embodiment 4
The present embodiment is used to illustrate two urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) 47.42 grams of lauryl amines and 22.93 grams of para-totuidine are added to 262 grams of 500SN and 150BS miscella
(100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) in, 80 DEG C are heated to, stirs 2 minutes, organic amine is melted completely；
(2) 55.65 grams of MDI are added in 252 grams of 500SN and 150BS miscella, are heated to 80 DEG C, are stirred 2 minutes,
MDI is set to melt completely；
(3) two groups of solution of step (1) and step (2) are mixed, at 90 DEG C, reacts 40min under 230rpm；
(4) when being warming up to 210 DEG C, constant temperature refining 5min；
(5) add 242 grams of 500SN and 150BS miscella, stirring is cooled to 130 DEG C, add 7.2 grams of S1,10.8 gram two
Thio dimethyl carbamic acid molybdenum, stirs under 230rpm；
(6) 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.8 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of two carbamido thickening agent 14, the weight % of base oil 84.
Comparative example 1
Two urea-base greases are prepared according to the method for embodiment 4, unlike, S1 is replaced with to the diphenylamines of equivalent.Production
Moral character can be as shown in table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight % of diphenylamines 0.8, two sulphur
For the weight % of dimethyl carbamic acid molybdenum 1.2, the weight % of two carbamido thickening agent 14, the weight % of base oil 84.
Embodiment 5
The present embodiment is used to illustrate four urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 282 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) arrived with 36.42 grams of TDI Hybrid Heatings
60 DEG C, 6.28 grams of ethylenediamines are added, are warming up to 80 DEG C, react 20min；
(2) by 260 grams of 500SN base oils and 56.3 grams of octadecylamine Hybrid Heatings to 60 DEG C；
(3) two groups of solution of step (1) and step (2) are mixed, reacts 20min at 80 DEG C；
(4) 180 DEG C are warming up to, constant temperature refining 25min；241 grams of 500SN base oils are added thereto, and stirring is cooled to 130
DEG C, 1.8 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred at 200 rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.2 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of four carbamido thickening agent 11.1, the weight % of base oil 87.5.
Embodiment 6
The present embodiment is used to illustrate four urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 282 grams of 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter) arrived with 45.08 grams of MDI Hybrid Heatings
50 DEG C, 5.41 grams of ethylenediamines are added, are warming up to 100 DEG C, react 60min；
(2) by 260 grams of 150BS base oils and 48.51 grams of octadecylamine Hybrid Heatings to 50 DEG C；
(3) two groups of solution of step (1) and step (2) are mixed, reacts 60min at 100 DEG C；
(4) 210 DEG C are warming up to, constant temperature refining 10min；241 grams of 150BS base oils are added thereto, and stirring is cooled to 90
DEG C, 9 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred under 180rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S11 weight %, two thio diformazans
Aminocarbamic acid molybdenum 1.2 weight %, the weight % of four carbamido thickening agent 11, the weight % of base oil 86.8.
Embodiment 7
The present embodiment is used to illustrate four urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 282 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 41.31 grams of TDI Hybrid Heatings
To 55 DEG C, 7.12 grams of ethylenediamines are added, are warming up to 95 DEG C, react 50min；
(2) by 260 grams of PAO6 synthetic hydrocarbon oils and 50.57 grams of octadecylamine Hybrid Heatings to 55 DEG C；
(3) two groups of solution of step (1) and step (2) are mixed, reacts 30min at 90 DEG C；
(4) 190 DEG C are warming up to, constant temperature refining 15min；241 grams of PAO6 synthetic hydrocarbon oils are added thereto, and stirring is cooled to
110 DEG C, 3.6 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred under 230rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.4 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of four carbamido thickening agent 11, the weight % of base oil 87.4.
Embodiment 8
The present embodiment is used to illustrate four urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 282 grams of 500SN and 150BS miscella, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) mixed with 50.2 grams of MDI
Conjunction is heated to 60 DEG C, adds 6.03 grams of ethylenediamines, is warming up to 90 DEG C, reacts 30min；
(2) by 260 grams of 500SN and 150BS miscella and 42.77 grams of octadecylamine Hybrid Heatings to 60 DEG C；
(3) two groups of solution of step (1) and step (2) are mixed, reacts 40min at 85 DEG C；
(4) 200 DEG C are warming up to, constant temperature refining 10min；241 grams of 500SN and 150BS miscella, stirring are added thereto
120 DEG C are cooled to, 7.2 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums is added, stirs at 300 rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.8 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of four carbamido thickening agent 11, the weight % of base oil 87.
Comparative example 2
Four urea-base greases are prepared according to the method for embodiment 8, unlike, S1 is replaced with to the diphenylamines of equivalent.Production
Moral character can be as shown in table 2.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight % of diphenylamines 0.8, two sulphur
For the weight % of dimethyl carbamic acid molybdenum 1.2, the weight % of four carbamido thickening agent 11, the weight % of base oil 87.
Embodiment 9
The present embodiment is used to illustrate six urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 199 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) arrived with 38.36 grams of MDI Hybrid Heatings
50℃；
(2) 199 grams of 500SN base oils and 41.27 grams of octadecylamine Hybrid Heatings are slowly added into step (1) to 50 DEG C
System in, be warming up to 80 DEG C of reaction 60min, be slowly added to 9.2 grams of ethylenediamines, 80 DEG C of reaction 60min of constant temperature；
(3) 188 grams of 500SN base oils and 19.17 grams of MDI Hybrid Heatings are slowly added into above-mentioned system to 50 DEG C,
80 DEG C of reaction 30min of constant temperature；
(4) 180 DEG C are warming up to, constant temperature refining 20min；188 grams of 500SN base oils are added thereto, and stirring is cooled to 130
DEG C, 1.8 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred at 200 rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.2 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of six carbamido thickening agent 12.1, the weight % of base oil 86.5.
Embodiment 10
The present embodiment is used to illustrate six urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 199 grams of 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter) arrived with 31.85 grams of TDI Hybrid Heatings
70℃；
(2) 199 grams of 150BS base oils and 49.24 grams of lauryl amine Hybrid Heatings are slowly added into step (1) to 70 DEG C
System in, be warming up to 100 DEG C of reaction 20min, be slowly added to 10.98 grams of ethylenediamines, 100 DEG C of reaction 20min of constant temperature；
(3) 188 grams of 150BS base oils and 15.93 grams of TDI Hybrid Heatings are slowly added into above-mentioned system to 70 DEG C,
100 DEG C of reaction 20min of constant temperature；
(4) 210 DEG C are warming up to, constant temperature refining 5min；188 grams of 150BS base oils are added thereto, and stirring is cooled to 90
DEG C, 9 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred under 180rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S11 weight %, two thio diformazans
Aminocarbamic acid molybdenum 1.2 weight %, the weight % of six carbamido thickening agent 12, the weight % of base oil 85.8.
Embodiment 11
The present embodiment is used to illustrate six urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 199 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 41.67 grams of MDI Hybrid Heatings
To 60 DEG C；
(2) 199 grams of PAO6 synthetic hydrocarbon oils and 35.5 grams of lauryl amine Hybrid Heatings are slowly added into step (1) to 60 DEG C
System in, be warming up to 95 DEG C of reaction 40min, be slowly added to 10 grams of ethylenediamines, 95 DEG C of reaction 40min of constant temperature；
(3) 188 grams of PAO6 synthetic hydrocarbon oils and 20.83 grams of MDI Hybrid Heatings are slowly added into above-mentioned system to 60 DEG C
In, 95 DEG C of reaction 40min of constant temperature；
(4) 190 DEG C are warming up to, constant temperature refining 15min；188 grams of PAO6 synthetic hydrocarbon oils are added thereto, and stirring is cooled to
100 DEG C, 3.6 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums are added, are stirred under 230rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.4 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of six carbamido thickening agent 12, the weight % of base oil 86.4.
Embodiment 12
The present embodiment is used to illustrate six urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 199 grams of 500SN and 150BS miscella, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) mixed with 35.19 grams of TDI
Conjunction is heated to 55 DEG C；
(2) 199 grams of 500SN and 150BS miscella and 43.08 grams of lauryl amine Hybrid Heatings are slowly added to 55 DEG C
Into the system of step (1), 90 DEG C of reaction 30min are warming up to, are slowly added to 12.13 grams of ethylenediamines, 90 DEG C of reactions of constant temperature
30min；
(3) 188 grams of 500SN and 150BS miscella and 17.6 grams of TDI Hybrid Heatings are slowly added into 55 DEG C
State in system, 90 DEG C of reaction 30min of constant temperature；
(4) 200 DEG C are warming up to, constant temperature refining 10min；188 grams of 500SN and 150BS miscella, stirring are added thereto
120 DEG C are cooled to, 7.2 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums is added, stirs at 300 rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.8 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of six carbamido thickening agent 12, the weight % of base oil 86.
Comparative example 3
Six urea-base greases are prepared according to the method for embodiment 12, unlike, S1 is replaced with to the diphenylamines of equivalent.Production
Moral character can be as shown in table 3.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight % of diphenylamines 0.8, two sulphur
For the weight % of dimethyl carbamic acid molybdenum 1.2, the weight % of six carbamido thickening agent 12, the weight % of base oil 86.
Embodiment 13
The present embodiment is used to illustrate eight urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 266 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) arrived with 57.59 grams of TDI Hybrid Heatings
50 DEG C, 9.93 grams of ethylenediamines are added, are warming up to 80 DEG C, after reaction 60 minutes, add 4.96 grams of ethylenediamines, 80 DEG C of constant temperature,
Reaction 60 minutes；
(2) by 252 grams of 500SN base oils and 44.52 grams of octadecylamine Hybrid Heatings to 50 DEG C, it is added to step (1) reaction
In system afterwards, 80 DEG C of constant temperature, react 60 minutes；
(3) 210 DEG C are warming up to, is kept for 5 minutes, adds 247 grams of 500SN base oils, stirring is cooled to 130 DEG C, adds
1.8 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums, stir under 180rpm；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 4.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.2 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of eight carbamido thickening agent 13.1, the weight % of base oil 85.5.
Embodiment 14
The present embodiment is used to illustrate eight urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 266 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter) with 68.1 grams of MDI Hybrid Heatings to 70
DEG C, 8.18 grams of ethylenediamines are added, are warming up to 100 DEG C, after reaction 20 minutes, add 4.08g ethylenediamines, 100 DEG C of constant temperature, instead
Answer 20 minutes；
(2) by 252 grams of 150BS base oils and 36.64 grams of octadecylamine Hybrid Heatings to 70 DEG C, it is added to step (1) reaction
In system afterwards, 100 DEG C of constant temperature, react 20 minutes；
(3) 180 DEG C are warming up to, is kept for 20 minutes, adds 247 grams of 150BS base oils, stirring is cooled to 90 DEG C, adds 9
Gram S1,10.8 grams of dithiodimethyl carbamic acid molybdenums, stirs at 300 rpm；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 4.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S11 weight %, two thio diformazans
Aminocarbamic acid molybdenum 1.2 weight %, the weight % of eight carbamido thickening agent 13, the weight % of base oil 84.8.
Embodiment 15
The present embodiment is used to illustrate eight urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 266 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 62.54 grams of TDI Hybrid Heatings
To 55 DEG C, 10.79 grams of ethylenediamines are added, are warming up to 90 DEG C, after reacting 40 minutes, add 5.39 grams of ethylenediamines, constant temperature 90
DEG C, react 40 minutes；
(2) by 252 grams of PAO6 synthetic hydrocarbon oils and 38.28 grams of lauryl amine Hybrid Heatings to 55 DEG C, it is added to step (1) reaction
In system afterwards, 90 DEG C of constant temperature, react 40 minutes；
(3) 190 DEG C are warming up to, is kept for 15 minutes, adds 247 grams of PAO6 synthetic hydrocarbon oils, stirring is cooled to 110 DEG C, added
Enter 3.6 grams of S1,10.8 grams of dithiodimethyl carbamic acid molybdenums, stir at 200 rpm；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 4.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.4 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of eight carbamido thickening agent 13.1, the weight % of base oil 85.3.
Embodiment 16
The present embodiment is used to illustrate eight urea-based lubricating grease compositions of the present invention and preparation method thereof.
(1) by 266 grams of 500SN and 150BS miscella, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) mixed with 72.85 grams of MDI
Conjunction is heated to 60 DEG C, adds 8.74 grams of ethylenediamines, is warming up to 95 DEG C, after reacting 30 minutes, adds 4.37 grams of ethylenediamines, permanent
95 DEG C of temperature, react 30 minutes；
(2) 252 grams of 500SN and 150BS miscella and 31.04 grams of lauryl amine Hybrid Heatings are added to step to 60 DEG C
Suddenly in (1) reacted system, 95 DEG C of constant temperature, react 30 minutes；
(3) 200 DEG C are warming up to, is kept for 10 minutes, adds 247 grams of 500SN and 150BS miscella, stirring is cooled to
100 DEG C, 7.2 grams of S1 are added, 10.8 grams of dithiodimethyl carbamic acid molybdenums, are stirred under 230rpm；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 4.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：S10.8 weight %, two thio two
Methyl carbamic acid molybdenum 1.2 weight %, the weight % of eight carbamido thickening agent 13, the weight % of base oil 85.
Comparative example 4
Eight urea-base greases are prepared according to the method for embodiment 4, unlike, S1 is replaced with to the diphenylamines of equivalent.Production
Moral character can be as shown in table 4.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight % of diphenylamines 0.8, two sulphur
For the weight % of dimethyl carbamic acid molybdenum 1.2, the weight % of eight carbamido thickening agent 13, the weight % of base oil 85.
Table 1
Table 2
Table 3
Table 4
It will be understood by those skilled in the art that dropping point is higher, the heat resistance of lubricating grease is better；Work cone penetration is got over
Small, the thickening performance of grease thickener is better；Extension work cone penetration is smaller, and the mechanical stability of lubricating grease is better；Oxidation
Initial temperature is higher, and the antioxygenic property of lubricating grease is better；Stencil oil-dividing value is smaller, and the colloid stability of lubricating grease is better；Water
Leaching number of dropouts is smaller, and the water resistance of lubricating grease is better.
Respectively by embodiment 4 compared with comparative example 1, by embodiment 8 compared with comparative example 2, by embodiment 12
Compared with comparative example 3, by embodiment 16 compared with comparative example 4, it can be seen that lubricating grease of the invention has more preferable
Heat resistance, mechanical stability, inoxidizability, colloid stability and water proofing property.
The urea-based lubricating grease composition of the present invention, due to containing antioxidant, drastically increases the antioxidant capacity of lubricating grease.
The lubricating grease of the present invention has splendid heat resistance, mechanical stability, inoxidizability, colloid stability and water proofing property etc., can
It is competent in the harsh working conditions such as high temperature, high speed, high load capacity, more water.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these 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 (12)
1. a kind of excellent urea-based lubricating grease composition of antioxygen property, on the basis of the weight of lubricant composition, the lubrication
Oil/fat composition includes following components：65-95 weight % lubricating base oil, 4-30 weight % carbamido thickening agent and 0.1-15 weights
Measure % additive, it is characterised in that the additive contains the compound of structure shown in formula (I)：
2. lubricant composition according to claim 1, wherein, on the basis of the weight of lubricant composition, the profit
Grease composition includes following components：70-90 weight % lubricating base oil, 4-28 weight % carbamido thickening agent and 1-10 weights
Measure % additive.
3. lubricant composition according to claim 1 or 2, wherein, on the basis of the weight of lubricant composition, formula
(I) content of the compound of structure shown in is 0.1-3 weight %.
4. lubricant composition according to claim 3, wherein, on the basis of the weight of lubricant composition, formula (I) institute
The content for showing the compound of structure is 0.2-1 weight %.
5. lubricant composition according to claim 1 or 2, wherein, the lubricating base oil be mineral oil, vegetable oil and
At least one of artificial oil.
6. lubricant composition according to claim 1 or 2, wherein, the carbamido thickening agent is amine and diisocyanate
Reaction product, the carbamido thickening agent be two carbamido thickening agents, four carbamido thickening agents, six carbamido thickening agents and eight urea groups thickening
At least one of agent.
7. lubricant composition according to claim 1 or 2, wherein, the additive also contains extreme pressure anti-wear additives.
8. lubricant composition according to claim 7, wherein, the extreme pressure anti-wear additives are two thio Acidic phosphates
Zinc, two thio dialkyl amido formic acid molybdenums, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), dibutyl two
At least one of thiocarbamic acid antimony, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide.
9. a kind of preparation method of the excellent urea-based lubricating grease composition of antioxygen property, methods described include：
(1) partial lubrication base oil, diisocyanate, amine hybrid reaction are generated into carbamido thickening agent；
(2) step (1) is reacted into gained system and is warming up to 180-210 DEG C, kept 5-25min, add remaining lubricating base oil,
Stirring is cooled to 90-130 DEG C, adds additive, is well mixed；
(3) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by two isocyanic acids
The dosage of carbamido thickening agent prepared by ester, amine is 4-30 weight %, and the dosage of additive is 0.1-15 weight %, and its feature exists
In the additive contains the compound of structure shown in formula (I)：
10. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, the use of lubricating base oil
The dosage of the carbamido thickening agent measure as 70-90 weight %, prepared by diisocyanate, amine is 4-28 weight %, the use of additive
Measure as 1-10 weight %.
11. the method according to claim 9 or 10, wherein, on the basis of the weight of lubricant composition, shown in formula (I)
The dosage of the compound of structure is 0.1-3 weight %.
12. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
The dosage of compound be 0.2-1 weight %.
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| EP0226308A2 (en) * | 1985-12-10 | 1987-06-24 | Mobil Oil Corporation | Benzotriazole derivatives and organic compositions containing same |
| US20080090743A1 (en) * | 2006-10-17 | 2008-04-17 | Mathur Naresh C | Compounds and methods of making the compounds |
| CN101368129A (en) * | 2008-08-06 | 2009-02-18 | 杭州得润宝油脂有限公司 | Urea grease composition and preparation method thereof |
| CN102504921A (en) * | 2011-10-27 | 2012-06-20 | 中国石油化工股份有限公司 | Polyurea-based grease additive composition |
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| EP0226308A2 (en) * | 1985-12-10 | 1987-06-24 | Mobil Oil Corporation | Benzotriazole derivatives and organic compositions containing same |
| US20080090743A1 (en) * | 2006-10-17 | 2008-04-17 | Mathur Naresh C | Compounds and methods of making the compounds |
| CN101368129A (en) * | 2008-08-06 | 2009-02-18 | 杭州得润宝油脂有限公司 | Urea grease composition and preparation method thereof |
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