CN105586137B - Excellent composite aluminum base grease composition of a kind of antioxygen property and preparation method thereof - Google Patents
Excellent composite aluminum base grease composition of a kind of antioxygen property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the composite aluminum base grease compositions 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 the lubricating base oil of 65 95 weight %, the composite aluminum base thickening agent of 5 35 weight % and 0.1 15 weight %, the additive contain the compound of structure shown in formula (I).The present invention also provides the preparation methods of the excellent composite aluminum base grease composition of antioxygen property.Lubricant composition provided by the invention has good mechanical stability, water-resistance and colloid stability, more has apparent advantage on antioxygenic property, and have good compatibility with other lubricating grease.The fat is enabled to be competent in the lubrication of various motors, generator, air blower, transportation, iron and steel enterprise and other various industrial equipments, the lubrication especially suitable for the friction part of mechanical equipment under various higher temperature wet conditions.
Description
Technical field
The present invention relates to lubricating grease fields, and in particular, to a kind of antioxygen property containing special additive is excellent to answer
Close aluminium-base grease composition and preparation method thereof.
Background technology
The research of composite aluminum base grease start from the 1950s, but be just taken seriously until the seventies, be mainly used for
The concentration of steel plant supplies fat system, and yield is only second to complex lithium grease and occupies second in complex-soap base grease.Composite aluminum base
Lubricating grease is a kind of high temperature multi-effect lubricating grease, has high dropping point and good multiple-effect performance, such as good colloid stability, oxidation
Stability, mechanical stability, water-resistance particularly with good pump-conveying property, are suitble to central system.Lee comes red et al. with just
Design method is handed over to find out stearic acid, benzoic acid and the optimum proportioning of aluminium isopropoxide, the clad aluminum for meeting professional standard has been made
Base grease；Cao Piye has studied influence of the basic component to composite aluminum base grease performance；Li Ye illuminates et al. have been inquired into various
Influence of the basic component of base oil and fat to the performance of fat tentatively proposes the optimum formula of composite aluminum base grease；
CN102021067A is prepared for a kind of suitable for barium aluminum lubricating grease for ships；CN102021068A is prepared for a kind of suitable for ship
Warship aluminium sodium base grease；CN1900244A introduces sulfoacid calcium, the composite aluminum base lubrication of preparation into composite aluminum base grease
Fat improves water-resistance, rust-preventing characteristic, extreme pressure property, mechanical stability and high temperature colloid stability in the case of not doping.
The service life of lubricating grease can shorten with temperature in use rising or the extension of lubrication time.It chemically says, makees in nature
Metal soap for thickening agent is the major reason for causing lubricating grease oxidation deterioration.In order to inhibit the oxidation deterioration of lubricating grease, prevent
Block product causes the corrosion of metal surface, to add in suitable antioxidant additive.At present, common antioxidant mainly divides
For two class of amine and phenols.Phenolic antioxidant generally comprises 2,6-di-tert-butyl p-cresol, 2,6- di-tert-butylphenols etc., but it makes
It is relatively low with temperature, generally within 150 DEG C.Amine antioxidants are mainly alkylated diphenylamine or alkylated phenyl-naphthylamines
Deng.
The content of the invention
The purpose of the invention is to meet the high request to the antioxygen property of lubricating grease, it is excellent to provide a kind of antioxygen property
Composite aluminum base 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 are the excellent performances such as anti-oxidant.
Therefore, to achieve these goals, on the one hand, the present invention provides the composite aluminum base profits that a kind of antioxygen property is excellent
Grease composition, on the basis of the weight of lubricant composition, the lubricant composition includes following components：65-95 weights
Measure lubricating base oil, the composite aluminum base thickening agent of 5-35 weight % and the additive of 0.1-15 weight % of %, the additive
Compound containing structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the lubricant composition includes following components：75-88
The additive of the lubricating base oil of weight %, the composite aluminum base thickening agent of 5-15 weight % and 0.1-5 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 present invention provides a kind of preparation sides of the excellent composite aluminum base grease composition of antioxygen property
Method, the described method includes：
(1) lubricating base oil of 1/5-2/5, higher fatty acids, silicon source heat temperature raising are subjected to saponification, then added in
The small molecule acid being dissolved in the lubricating base oil of 1/10-1/5 carries out recombination reaction；
(2) plus water cools down, and then heats to 200-220 DEG C and is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) ground 2-4 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 advanced
The dosage of composite aluminum base thickening agent prepared by aliphatic acid, small molecule acid and silicon source is 5-35 weight %, and the dosage of additive is
0.1-15 weight %, which is characterized in that the additive contains 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 75-88 weight %, by height
The dosage of composite aluminum base thickening agent prepared by grade aliphatic acid, small molecule acid and silicon source is 5-15 weight %, and the dosage of additive is
0.1-5 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 %.
Lubricant composition provided by the invention has good mechanical stability, water-resistance and colloid stability, more exists
There is apparent advantage on antioxygenic property, and have good compatibility with other lubricating grease.The fat is competent in various
Motor, generator, air blower, transportation, the lubrication of iron and steel enterprise and other various industrial equipments, especially suitable for various
The lubrication of the friction part of mechanical equipment under higher temperature wet condition.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
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.
Specific embodiment
The specific 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 present invention provides the composite aluminum base grease composition that a kind of antioxygen property is excellent, with the weight of lubricant composition
On the basis of amount, lubricant composition includes following components：The lubricating base oil of 65-95 weight %, the clad aluminum of 5-35 weight %
The additive of base thickening agent and 0.1-15 weight %, additive contain 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 the lubricating base oil of 75-88 weight %, the composite aluminum base thickening agent of 5-15 weight % and 0.1-5 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 contain the compound of structure shown in formula (I) by the additive in composite aluminum base grease composition
And realize goal of the invention, even if composite aluminum base grease composition has the excellent performances such as anti-oxidant.Therefore, for clad aluminum
The selection of each conventional constituents, does not limit specifically in base grease.
In the present invention, lubricating base oil can be lubricating base oil commonly used in the art, such as can be mineral oil,
At least one of vegetable oil and synthetic oil.100 DEG C of kinematic viscosity of lubricating base oil are preferably 5-60mm2/ s, more preferably 10-
30mm2/s.For the specific species of mineral oil, vegetable oil and synthetic oil, also there is no particular limitation, and it is normal that this field may be employed
Mineral oil, vegetable oil and synthetic 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., synthetic oil can be poly-a-olefin oil (PAO), Esters oil, fluorine
At least one of oil and silicone oil etc..
In the present invention, composite aluminum base thickening agent can be composite aluminum base thickening agent commonly used in the art, for example, can be acid
It reacts and generates with silicon source, acid includes higher fatty acids and small molecule acid.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, be preferably lauric acid, palmitic acid, stearic acid and 12-
At least one of hydroxy stearic acid, more preferably stearic acid and/or 12- hydroxy stearic acids.
Wherein, small molecule acid is preferably the carboxylic acid of C4-C11, more preferably benzoic acid, terephthalic acid (TPA), azelaic acid and the last of the ten Heavenly stems
At least one of diacid.
Wherein, silicon source is preferably aluminium isopropoxide and/or aluminium isopropoxide tripolymer.
Above-mentioned composite aluminum base thickening agent may be employed the thinkable various methods of those skilled in the art institute and obtain.
In the present invention, since the antioxidant of structure shown in formula (I) and other additives have preferable compatibility,
According to the use needs of lubricating grease, additive of the invention can also contain antirust agent.For antirust agent species and content without
The species and content of this field routine may be employed in particular/special requirement.For example, antirust agent can be barium mahogany sulfonate, dinonyl benzene
At least one of barium sulfonate and Lanolin Calcium Soap, the content of antirust agent can account for the 0.05-4.5 of lubricant composition total weight
Weight % is preferably 0.1-2 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 with bromide reagent is contacted and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product that step (b) obtains is made to be contacted with formula (IV) compound represented and carries 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 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 inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
It will be understood by those skilled in the art that in order to carry out stable reaction, 0.5-1.5h is reacted 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, and reaction system itself is made to be to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethyl alcohol, n,N-Dimethylformamide and acetonitrile
Kind, methanol and/or acetonitrile are more preferably, is 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 molar 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, purer intermediate M, goes back in order to obtain
It needing to post-process the system after reaction, the mode of post processing can include solvent is removed under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, the system after reaction 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 are added at 15-30 DEG C, keep 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 being protected from light, intermediate M that step (a) obtains is reacted with bromide reagent at 15-30 DEG C
Then 1-2h is quenched with quencher.
" inert atmosphere " is as previously mentioned, details are not described herein.
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 salt solution.
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 molar 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 the molal quantity of intermediate M,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the method for the present invention 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 is not construed as limiting the scope of the present invention using NBS, purpose by way of example only.
In step (b) of the present invention, in addition to the bromination product shown in generation formula (III), there is the bromo production at micro ortho position
Object generates, and is generated without the bromination product of meta position, but the amount of the bromination product at ortho position very pettiness, to subsequent reactions without substantive shadow
It rings, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, purer bromination product in order to obtain,
It also needs to post-process the system after being quenched, the mode of post processing can include washing, drying, solvent, example is removed under reduced pressure
Such as, the system after being quenched is washed with distilled water, it is dry that anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C
Drying prescription keeps 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 formula (IV) compound represented are reacted at 80-100 DEG C
4-8h。
" inert atmosphere " is as previously mentioned, details are not described herein.
In the present invention, in order to carry out stable reaction, 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, ligand and alkali.Palladium salt is preferably selected from palladium and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3]；Ligand 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, bromination product and the dosage of formula (IV) compound represented that step (b) obtains are substantially
For equimolar amounts, but formula (IV) compound represented can be suitably excessive.Shown in the bromination product and formula (IV) that step (b) obtains
The molar 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 ligand
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 is contacted with formula (IV) compound represented 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 purer final product, i.e. antioxygen shown in formula (I) in order to obtain
Agent, the method for the present invention, which preferably further includes, post-processes the system after reaction, and the mode of post processing can include filtering, solvent
Dilution washes, is dry, solvent is removed under reduced pressure, for example, the filtrate after the system filtering after reaction to be poured into the second of 1-10 times of volume
It in acetoacetic ester (or dichloromethane), is then washed with distilled water, anhydrous calcium chloride or anhydrous sulphur is 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 preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, 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 solvent dosage of this field routine, this is known to those skilled in the art, herein no longer without particular/special requirement
It repeats.
As described above, it is contemplated that knot shown in formula (I) is contained by the additive in composite aluminum base grease composition
The compound of structure and realize goal of the invention, even if lubricant composition has the excellent performances such as anti-oxidant.Therefore, for compound
Without particular/special requirement method commonly used in the art may be employed, for example, second aspect, sheet in the preparation method of aluminium-base grease
Invention additionally provides a kind of preparation method of the excellent composite aluminum base grease composition of antioxygen property, and this method includes：
(1) lubricating base oil of 1/5-2/5, higher fatty acids, silicon source heat temperature raising are subjected to saponification, then added in
The small molecule acid being dissolved in the lubricating base oil of 1/10-1/5 carries out recombination reaction；
(2) plus water cools down, and then heats to 200-220 DEG C and is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) ground 2-4 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 advanced
The dosage of composite aluminum base thickening agent prepared by aliphatic acid, small molecule acid and silicon source is 5-35 weight %, and the dosage of additive is
0.1-15 weight %, additive contain the compound of structure shown in formula (I)：
In the method for the present invention, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 75-
88 weight %, the dosage of the composite aluminum base thickening agent prepared by higher fatty acids, small molecule acid and silicon source are 5-15 weight %, are added
The dosage for adding agent is 0.1-5 weight %.
In the method for the present invention, the molar ratio of the total amount and silicon source of higher fatty acids and small molecule acid is preferably stoichiometry
Than silicon source can also excess 1-10 weight %.The molar ratio of higher fatty acids and small molecule acid is preferably 1:0.1-5, more preferably
For 1:0.3-2.It will be understood by those skilled in the art that it is answered according to what is prepared by higher fatty acids, small molecule acid and silicon source
The dosage of aluminium base thickening agent is closed, counter can release the dosage of higher fatty acids, small molecule acid and silicon source, this is people in the art
Well known to member, details are not described herein.
In the method for the present invention, 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 % as, more preferably 0.2-1 weight %.
In the method for the present invention, the lubricating base oil of 1/5-2/5, the lubricating base oil of 1/10-1/5 refer respectively to account for lubrication base
1/5-2/5,1/10-1/5 of plinth oil total amount.
In the method for the present invention step (1), 90-120 DEG C is preferably heated to, the saponification time is preferably 0.5-
1.5h, complex reaction time are preferably 0.5-1.5h.
In the method for the present invention step (2), add the amount of water temperature is preferably made to be down to 70-90 DEG C, and preferably keep the temperature 5-25min.
In the method for the present invention step (2), the time of refining is preferably 5-25min.
Each step of the method for the present invention preferably carries out under stiring, can be this field for mixing speed without particular/special requirement
Conventional mixing speed, for example, mixing speed can be 20-500rpm.
Lubricating base oil, higher fatty acids, small molecule acid, silicon source, additive are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
The physico-chemical analysis method of product：Constituent content is measured 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.
Preparation example
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds in 150ml
Methanol and 0.01mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyls of 0.1mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.3mol.React 1 it is small when after remove ice-water bath, 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Flow 2 it is small when after stop reaction, the system after reaction is steamed into solvent at 0.03MPa, 50 DEG C, then add in 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 in 10g
Calcium chloride dry 20min, filtrate after filtering at 25 DEG C are evaporated off solvent under 40 DEG C, 0.03MPa, obtain midbody product
M1。
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds in 150ml
Dry tetrahydrofuran, then dissolve in midbody product M1, and add in the ammonium nitrate of 0.05mol, under the conditions of being protected from light slowly plus
Enter 0.1mol brominated reagents NBS.1.5h is stirred to react at 25 DEG C, is then quenched with saturated salt solution, is then distilled with 100ml
Water (twice) washs, and adds in 10g anhydrous sodium sulfates dry 20min 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 in the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds in 150ml
Dichloromethane as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.12mol, then add in
The tri-tert phosphorus of 0.02mol, the sodium tert-butoxide of 0.02mol and the Pd (OAc) of 0.005mol2.90 DEG C are gradually heating to, is continued
Stir 6h.Then the filtrate after the system filtering after reaction is added in into 250ml ethyl acetate, and be transferred in separatory funnel, used
100ml distilled water (twice) washs, and adds in 10g anhydrous sodium sulfates dry 20min at 25 DEG C.Filtrate after filtering is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
The physico-chemical analysis data of S1 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 can be seen that S1 with the knot shown in formula (I)
Structure.
Embodiment 1
The present embodiment is used to illustrate composite aluminum base grease composition of the present invention and preparation method thereof.
(1) by 135.8 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter), 10.5 grams of stearic acid and 7.2 grams
Aluminum isopropylate is added in fat kettle processed, is heated to 110 DEG C under 200rpm stirrings, is carried out saponification 1h, then will be molten
4.5 gram benzoic acid of the solution in 45.2 grams of 500SN base oils, which add in, carries out recombination reaction 1h in fat kettle processed；
(2) plus water is cooled to 90 DEG C, keeps 5min, continues stirring and is warming up to 210 DEG C, heat preservation refining 5min；
(3) 90.5 grams of 500SN base oils are added in, treats that temperature is cooled to 110 DEG C, adds in 2 grams of S1,2.5 grams of barium mahogany sulfonates,
It stirs evenly at 200 rpm；
(4) 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：Compound 7 weight % of aluminium soap；Lubrication
91 weight % of base oil；S11 weight %；1 weight % of barium mahogany sulfonate.
Embodiment 2
The present embodiment is used to illustrate composite aluminum base grease composition of the present invention and preparation method thereof.
(1) by 134 grams of 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter), 13.98 grams of stearic acid and 9.36 grams
Aluminum isopropylate is added in fat kettle processed, is heated to 90 DEG C under 60rpm stirrings, is carried out saponification 1.5h, then will be molten
6 gram benzoic acid of the solution in 42 grams of 150BS base oils, which add in, carries out recombination reaction 1.5h in fat kettle processed；
(2) plus water is cooled to 70 DEG C, keeps 25min, continues stirring and is warming up to 220 DEG C, heat preservation refining 8min；
(3) 88 grams of 150BS base oils are added in, treats that temperature is cooled to 100 DEG C, adds in 2 grams of S1,2.5 grams of barium mahogany sulfonates,
It is stirred evenly under 60rpm；
(4) 4 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：Compound 9 weight % of aluminium soap；Lubrication
89.5 weight % of base oil；S10.7 weight %；0.8 weight % of barium mahogany sulfonate.
Embodiment 3
The present embodiment is used to illustrate composite aluminum base grease composition of the present invention and preparation method thereof.
(1) by 145 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter), 11.3 grams of stearic acid and 5.9 gram three
Aluminium isopropoxide is added in fat kettle processed, is heated to 100 DEG C under 300rpm stirrings, is carried out saponification 1.2h, then will be molten
4.9 gram benzoic acid of the solution in 35 grams of PAO6 synthetic hydrocarbon oils, which add in, carries out recombination reaction 1.2h in fat kettle processed；
(2) plus water is cooled to 80 DEG C, keeps 15min, continues stirring and is warming up to 200 DEG C, heat preservation refining 25min；
(3) 88 grams of PAO6 synthetic hydrocarbon oils are added in, treats that temperature is cooled to 105 DEG C, adds in 2 grams of S1,2.5 grams of barium mahogany sulfonates,
It stirs evenly at 300 rpm；
(4) 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：Compound 7 weight % of aluminium soap；Lubrication
92 weight % of base oil；S10.4 weight %；0.6 weight % of barium mahogany sulfonate.
Embodiment 4
The present embodiment is used to illustrate composite aluminum base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 146 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter), 8.4 grams of stearic acid and
5.4 grams of aluminum isopropylates are added in fat kettle processed, are heated to 120 DEG C under 500rpm stirrings, are carried out saponification 0.5h, so
3.6 grams of benzoic acid being dissolved in afterwards in the miscella of 40 grams of 500SN and 150BS add in fat kettle processed and carry out recombination reaction
0.5h；
(2) plus water is cooled to 85 DEG C, keeps 10min, continues stirring and is warming up to 205 DEG C, heat preservation refining 15min；
(3) miscella of 90 grams of 500SN and 150BS is added in, treats that temperature is cooled to 130 DEG C, adds in 2 grams of S1,3 grams of oil sulphurs
Sour barium, stirs evenly at 500 rpm；
(4) 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：Compound 6.5 weight % of aluminium soap；Profit
93 weight % of sliding base oil；S10.2 weight %；0.3 weight % of barium mahogany sulfonate.
Comparative example 1
Method according to embodiment 4 prepares composite aluminum base grease, unlike, S1 is replaced with to the diphenylamines of equivalent.
Properties of product are as shown in table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：Compound 6.5 weight % of aluminium soap；Profit
93 weight % of sliding base oil；0.2 weight % of diphenylamines；0.3 weight % of barium mahogany sulfonate.
Table 1
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Oxidation stability：SH/T
0325；Stencil oil-dividing：SH/T 0324；Anticorrosive property：GB/T 5018；Water drenches number of dropouts：SH/T 0109；Copper corrosion：GB/T
7326。
It will be understood by those skilled in the art that work cone penetration is smaller, the thickening performance of grease thickener is better；
Oxidation stability is smaller, 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.
By embodiment 4 compared with comparative example 1 as can be seen that the present invention lubricating grease have better inoxidizability,
Colloid stability and water proofing property.
Lubricant composition provided by the invention has good mechanical stability, water-resistance and colloid stability, more exists
There is apparent advantage on antioxygenic property, and have good compatibility with other lubricating grease.The fat is competent in various
Motor, generator, air blower, transportation, the lubrication of iron and steel enterprise and other various industrial equipments, especially suitable for various
The lubrication of the friction part of mechanical equipment under higher temperature wet condition.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, 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 also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of excellent composite aluminum base grease composition of antioxygen property, described on the basis of the weight of lubricant composition
Lubricant composition includes following components：The lubricating base oil of 65-95 weight %, the composite aluminum base thickening agent of 5-35 weight % and
The additive of 0.1-15 weight %, which is characterized 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：The lubricating base oil of 75-88 weight %, the composite aluminum base thickening agent of 5-15 weight % and
The additive of 0.1-5 weight %.
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 is mineral oil, vegetable oil and
At least one of synthetic oil.
6. lubricant composition according to claim 1 or 2, wherein, the composite aluminum base thickening agent is anti-with silicon source for acid
It should generate, the acid includes higher fatty acids and small molecule acid.
7. lubricant composition according to claim 6, wherein, the higher fatty acids is the aliphatic acid of C12-C25, institute
State the carboxylic acid that small molecule acid is C4-C11.
8. lubricant composition according to claim 7, wherein, the higher fatty acids is lauric acid, palmitic acid, tristearin
At least one of acid and 12- hydroxy stearic acids, the small molecule acid is benzoic acid, terephthalic acid (TPA), azelaic acid and decanedioic acid
At least one of.
9. lubricant composition according to claim 8, wherein, the higher fatty acids is stearic acid and/or 12- hydroxyls
Stearic acid.
10. lubricant composition according to claim 6, wherein, source of aluminium is aluminium isopropoxide and/or aluminium isopropoxide three
Aggressiveness.
11. lubricant composition according to claim 1 or 2, wherein, the additive also contains antirust agent.
12. lubricant composition according to claim 11, wherein, the antirust agent is barium mahogany sulfonate, dinonyl benzene
At least one of barium sulfonate and Lanolin Calcium Soap.
13. a kind of preparation method of the excellent composite aluminum base grease composition of antioxygen property, the described method includes：
(1) lubricating base oil of 1/5-2/5, higher fatty acids, silicon source heat temperature raising are subjected to saponification, then add in dissolving
Small molecule acid in the lubricating base oil of 1/10-1/5 carries out recombination reaction；
(2) plus water cools down, and then heats to 200-220 DEG C and is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) ground 2-4 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 higher aliphatic
The dosage of composite aluminum base thickening agent prepared by acid, small molecule acid and silicon source is 5-35 weight %, and the dosage of additive is 0.1-15
Weight %, which is characterized in that the additive contains the compound of structure shown in formula (I)：
14. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
Dosage is 75-88 weight %, the dosage of the composite aluminum base thickening agent prepared by higher fatty acids, small molecule acid and silicon source is 5-15
Weight %, the dosage of additive is 0.1-5 weight %.
15. the method according to claim 13 or 14, 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 %.
16. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
Compound dosage be 0.2-1 weight %.
17. the method according to claim 13 or 14, wherein, the total amount and silicon source of higher fatty acids and small molecule acid are rubbed
You are than being stoichiometric ratio；The molar ratio of higher fatty acids and small molecule acid is 1:0.1-5.
18. according to the method for claim 17, wherein, the molar ratio of higher fatty acids and small molecule acid is 1:0.3-2.
19. the method according to claim 13 or 14, wherein, in step (1), 90-120 DEG C is heated to, saponification is anti-
It is 0.5-1.5h, complex reaction time 0.5-1.5h between seasonable.
20. the method according to claim 13 or 14, wherein, in step (2), add the amount of water temperature is made to be down to 70-90 DEG C,
And keep the temperature 5-25min.
21. the method according to claim 13 or 14, wherein, in step (2), the time of the refining is 5-25min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| CN1160754A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Composite barium-base grease and its preparation |
| CN103013628A (en) * | 2012-12-27 | 2013-04-03 | 深圳市优宝惠新材料科技有限公司 | Complex aluminum-based grease composition and preparation method thereof |
-
2014
- 2014-10-23 CN CN201410573340.3A patent/CN105586137B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| CN1160754A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Composite barium-base grease and its preparation |
| CN103013628A (en) * | 2012-12-27 | 2013-04-03 | 深圳市优宝惠新材料科技有限公司 | Complex aluminum-based grease composition and preparation method thereof |
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