CN105586113B - Excellent sodium base grease composition of a kind of antioxygen property and preparation method thereof - Google Patents
Excellent sodium base grease composition of a kind of antioxygen property and preparation method thereof Download PDFInfo
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- CN105586113B CN105586113B CN201410573339.0A CN201410573339A CN105586113B CN 105586113 B CN105586113 B CN 105586113B CN 201410573339 A CN201410573339 A CN 201410573339A CN 105586113 B CN105586113 B CN 105586113B
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- CTBYJITWIRIDID-UHFFFAOYSA-N CC(C)(C)c1cc(Cc(cc2)ccc2NC2=CCC(C[n]3nnc4c3cccc4)C=C2)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(Cc(cc2)ccc2NC2=CCC(C[n]3nnc4c3cccc4)C=C2)cc(C(C)(C)C)c1O CTBYJITWIRIDID-UHFFFAOYSA-N 0.000 description 1
- IERZEVFTXXSUFS-UHFFFAOYSA-N CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O IERZEVFTXXSUFS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses the sodium 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 sodium base thickening agent of 4 30 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 sodium base grease composition of antioxygen property.Lubricant composition provided by the invention has good 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 various ball bearings such as high speed, middling speed.
Description
Technical field
The present invention relates to lubricating grease fields, and in particular, to a kind of excellent sodium of antioxygen property containing special additive
Base grease composition and preparation method thereof.
Background technology
Sodium base grease is usually to be made by natural animal-plant grease soda soap or fatty acid sodium soap thickening mineral oil, is had
Higher dropping point, good colloid stability, shear stability.In process of production by changing raw materials for production and preparation process
The product of different appearances and different performance can be made in condition.
CN102021546A reports a kind of aqueous rust preventive for firm product antirust；CN101153236 divides different-grain diameter
The solid powder of cloth is added in lubricating grease, not only increases the water repelling property of lubricating grease, also improves extreme pressure anti-wear；
CN1557922 is prepared for the aqueous sodium base grease containing 8-30% clean waters by adding clean water into sodium base grease,
The fat is a kind of substantially pollution-free to environment, high lubricating effect, has thermal balance to act on and of low cost can be suitable for heavy burden
The lubriation material of lotus sliding bearing；CN102021068A is prepared for a kind of sodium aluminate soap grease for ship, suitable for Ship Propeling
Device and Floating Crane and dredger, 75 DEG C of dropping point or more have good water-resistance, protective and rust-preventing characteristic, existing appropriate
Trace is lubricated, and has corrosion-resisting function, and has the function of to lower mechanicalness noise；US2468098 is containing 5-35% aliphatic acid
0.1-5% acrylic acid sodium salts are added in the lubricating grease of soda soap, reduce the solubility of soda soap in water；Morway in US2591586
Et al. find that methacrylaldehyde and its derivative also can prepare sodium base grease with polymer acid.
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
Sodium 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 sodium base greases 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, the sodium base thickening agent of 4-30 weight % 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 the lubricating base oil of weight %, the sodium base thickening agent of 4-28 weight % 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 present invention provides a kind of preparation method of the excellent sodium base grease composition of antioxygen property, institutes
The method of stating includes：
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, 70-90 DEG C is warming up to, adds in hydroxide
Sodium carries out saponification, then optionally, adds in small molecule acid and carries out recombination reaction；
(2) 100-120 DEG C is warming up to, adds in the lubricating base oil of 1/5-2/5,180-220 DEG C is warming up to and is refined；
(3) remaining lubricating base oil is added in, 80-100 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 sodium base thickening agent prepared by aliphatic acid, optional small molecule acid and sodium hydroxide is 4-30 weight %, the use of additive
It measures as 0.1-15 weight %, 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 70-90 weight %, by height
The dosage of sodium base thickening agent prepared by grade aliphatic acid, optional small molecule acid and sodium hydroxide is 4-28 weight %, additive
Dosage 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 %.
Lubricant composition provided by the invention has good colloid stability, more has on antioxygenic property apparent
Advantage, and have good compatibility with other lubricating grease.Enable the fat be competent in various motors, generator, air blower,
The lubrication of transportation, iron and steel enterprise and other various industrial equipments, especially suitable for the various ball bearings such as high speed, middling speed
Lubrication.
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 sodium base grease composition that a kind of antioxygen property is excellent, using the weight of lubricant composition as
Benchmark, lubricant composition include following components：The lubricating base oil of 65-95 weight %, the sodium base thickening agent of 4-30 weight %
With the additive of 0.1-15 weight %, 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 the lubricating base oil of 70-90 weight %, the sodium base thickening agent of 4-28 weight % 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 sodium base grease composition
Existing goal of the invention, even if sodium base grease composition has the excellent performances such as anti-oxidant.Therefore, for each in sodium base grease
The selection of conventional constituents, does not limit specifically.
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, sodium base thickening agent can be sodium base thickening agent commonly used in the art, for example, can be acid and hydroxide
Sodium reaction generation, acid include higher fatty acids and optional small molecule acid.
In the present invention, " optional ", which refers to have, not to be had." optional small molecule acid " refers to that small molecule acid is
A kind of optional component can include the component, can not also include the component, i.e. sodium base thickening agent of the invention can be by
Higher fatty acids is generated with sodium hydroxide reaction, can also be generated by higher fatty acids and small molecule acid with sodium hydroxide reaction.
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.
It will be understood by those skilled in the art that in actual use, sodium hydrate aqueous solution is generally added in, for hydrogen
The concentration of aqueous solution of sodium oxide is without particular/special requirement, such as can be 1-30 weight %.
Above-mentioned sodium 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 0.01-4.5 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 structure shown in formula (I) is contained by the additive in sodium base grease composition
Compound and realize goal of the invention, even if lubricant composition has the excellent performances such as anti-oxidant.Therefore, lubricated for sodium base
Without particular/special requirement method commonly used in the art may be employed, for example, second aspect, the present invention also carries in the preparation method of fat
A kind of preparation method for the sodium base grease composition for having supplied antioxygen property excellent, this method include：
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, 70-90 DEG C is warming up to, adds in hydroxide
Sodium carries out saponification, then optionally, adds in small molecule acid and carries out recombination reaction；
(2) 100-120 DEG C is warming up to, adds in the lubricating base oil of 1/5-2/5,180-220 DEG C is warming up to and is refined；
(3) remaining lubricating base oil is added in, 80-100 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 sodium base thickening agent prepared by aliphatic acid, optional small molecule acid and sodium hydroxide is 4-30 weight %, the use of additive
It measures as 0.1-15 weight %, additive contains 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 70-
90 weight %, the dosage of the sodium base thickening agent prepared by higher fatty acids, optional small molecule acid and sodium hydroxide are 4-28 weights
% is measured, the dosage of additive is 1-10 weight %.
In the method for the present invention, the molar ratio of the total amount and sodium hydroxide of higher fatty acids and optional small molecule acid is preferably
Stoichiometric ratio, sodium hydroxide can also excess 1-10 weight %.The molar ratio of higher fatty acids and optional small molecule acid is excellent
Elect 1 as:0.1-1.It will be understood by those skilled in the art that according to by higher fatty acids, optional small molecule acid and hydrogen-oxygen
Change the dosage of sodium base thickening agent prepared by sodium, counter can release the dosage of higher fatty acids, small molecule acid and sodium hydroxide, this is
Known to one of skill in the art, details are not described herein.
In the present invention, can also not have as previously mentioned, " optional " refers to have.In step (1), " and then optionally, add
Enter small molecule acid and carry out recombination reaction " refer to that " add in small molecule acid progress recombination reaction " is an optional step, it can be with
Including the step, the step can not also be included；It is a kind of optional component that " optional small molecule acid ", which refers to small molecule acid,
It can include the component, the component can not also be included；" the total amount and sodium hydroxide of higher fatty acids and optional small molecule acid
Molar ratio be stoichiometric ratio " refer to that, when not containing small molecule acid, the molar ratio of higher fatty acids and sodium hydroxide is excellent
Elect stoichiometric ratio as, when containing small molecule acid, the molar ratio of the total amount and sodium hydroxide of higher fatty acids and small molecule acid
Preferably stoichiometric ratio." molar ratio of higher fatty acids and optional small molecule acid is 1:0.1-1 " refers to when containing small
During molecule acid, the molar ratio of higher fatty acids and small molecule acid is preferably 1:0.1-1.In short, those skilled in the art should manage
Solution, sodium base thickening agent of the invention can be generated by higher fatty acids and sodium hydroxide reaction, can also be by higher aliphatic
Acid and small molecule acid are generated with sodium hydroxide reaction.
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 refers to the 1/5-2/5 for accounting for lubricating base oil total amount.
In the method for the present invention step (1), saponification temperature is preferably 100-110 DEG C, and the saponification time is preferably 1-
3h, optional complex reaction time are preferably 1-3h." optional complex reaction time is preferably 1-3h " refers to multiple when including
When closing reaction step, complex reaction time is preferably 1-3h.
In the method for the present invention step (2), the time of refining is preferably 5-20min.
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 20-400rpm.
Lubricating base oil, higher fatty acids, small molecule acid, 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 sodium base grease composition of the present invention and preparation method thereof.
(1) by 120 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter) add with 8.96 grams of 12- hydroxy stearic acids
Enter in fat kettle processed, the agitating and heating under 180rpm, be warming up to 80 DEG C, adding in the aqueous solution containing 2 grams of sodium hydroxides, (concentration is 8 weights
Measure %), 100 DEG C are warming up to, carries out saponification 3h；
(2) 120 DEG C are warming up to, adds in 120 grams of 150BS base oils, is warming up to 200 DEG C, refines 5min；
(3) 120 grams of 150BS base oils are added in, stirring is cooled to 100 DEG C, adds in 0.8 gram of S1,0.7 gram of barium mahogany sulfonate,
It is stirred evenly under 180rpm；
(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：12- hydroxyl sodium stearates 9.62
Weight %；90 weight % of lubricating base oil；S10.2 weight %；0.18 weight % of barium mahogany sulfonate.
Embodiment 2
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by 84 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) add with 25.5 grams of 12- hydroxy stearic acids
Enter in fat kettle processed, at 200 rpm agitating and heating, be warming up to 70 DEG C, add in the aqueous solution (concentration 15 containing 3.6 grams of sodium hydroxides
Weight %), 95 DEG C are warming up to, carries out saponification 1h；
(2) 100 DEG C are warming up to, adds in 34 grams of 500SN base oils, is warming up to 180 DEG C of refining 10min；
(3) 42 grams of 500SN base oils are added in, stirring is cooled to 90 DEG C, adds in 1.1 grams of S1,3.8 grams of barium mahogany sulfonates,
It is stirred evenly under 200rpm；
(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：15 weight of 12- hydroxyl sodium stearates
Measure %；82.4 weight % of lubricating base oil；S10.6 weight %；2 weight % of barium mahogany sulfonate.
Embodiment 3
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by 75 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 21.5 grams of stearic acid addition fat processed
In kettle, agitating and heating, is warming up to 90 DEG C at 300 rpm, and adding in the aqueous solution containing 3.1 grams of sodium hydroxides, (concentration is 18 weights
Measure %), 105 DEG C are warming up to, carries out saponification 2h；
(2) 110 DEG C are warming up to, adds in 35 grams of PAO6 synthetic hydrocarbon oils, is warming up to 220 DEG C of refining 15min；
(3) 25 grams of PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 80 DEG C, adds in 1.3 grams of S1,1.6 grams of barium mahogany sulfonates,
It is stirred evenly under 300rpm；
(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：15.2 weight % of odium stearate；
83 weight % of lubricating base oil；S10.8 weight %；1 weight % of barium mahogany sulfonate.
Embodiment 4
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 24.6 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) and 14.85 grams of tristearin
Acid is added in fat kettle processed, the agitating and heating under 230rpm, is warming up to 85 DEG C, and adding in the aqueous solution containing 2 grams of sodium hydroxides, (concentration is
30 weight %), 100 DEG C are warming up to, carries out saponification 3h；
(2) 120 DEG C are warming up to, adds in the miscella of 24.6 grams of 500SN and 150BS, is warming up to 210 DEG C of refining 20min；
(3) miscella of 32.8 grams of 500SN and 150BS is added in, stirring is cooled to 85 DEG C, adds in 1 gram of S1,1 gram of oil sulphur
Sour barium stirs evenly under 230rpm；
(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：16 weight % of odium stearate；Profit
82 weight % of sliding base oil；S11 weight %；1 weight % of barium mahogany sulfonate.
Comparative example 1
Method according to embodiment 4 prepares sodium base grease, unlike, S1 is replaced with to the diphenylamines of equivalent.Product
Performance is as shown in table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：16 weight % of odium stearate；Profit
82 weight % of sliding base oil；1 weight % of diphenylamines；1 weight % of barium mahogany sulfonate.
Embodiment 5
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by 275 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and 128.02 grams of stearic acid addition systems
In fat kettle, the agitating and heating under 180rpm is warming up to 80 DEG C, and adding in the aqueous solution containing 32.4 grams of sodium hydroxides, (concentration is 22 weights
Measure %), 100 DEG C are warming up to, carries out saponification 3h, then 43.96 grams of benzoic acid are added in into system, carry out recombination reaction 3h；
(2) 120 DEG C are warming up to, adds in 265 grams of 500SN base oils, is warming up to 200 DEG C, refines 5min；
(3) 257 grams of 500SN base oils are added in, stirring is cooled to 100 DEG C, adds in 10 grams of S1,7 grams of barium mahogany sulfonates,
It is stirred evenly under 180rpm；
(4) 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：13.8 weight % of odium stearate；
5.2 weight % of sodium benzoate；79.3 weight % of lubricating base oil；S11 weight %；0.7 weight % of barium mahogany sulfonate.
Embodiment 6
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by 270 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter) and 142.24 grams of stearic acid addition systems
In fat kettle, agitating and heating, is warming up to 70 DEG C at 200 rpm, and adding in the aqueous solution containing 32 grams of sodium hydroxides, (concentration is 15 weights
Measure %), 110 DEG C are warming up to, carries out saponification 1h, then 36.64 grams of benzoic acid are added in into system, carry out recombination reaction 1h；
(2) 100 DEG C are warming up to, adds in 260 grams of 150BS base oils, is warming up to 180 DEG C, refines 10min；
(3) 259 grams of 150BS base oils are added in, stirring is cooled to 90 DEG C, adds in 4 grams of S1,7 grams of barium mahogany sulfonates,
It is stirred evenly under 200rpm；
(4) 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：15.4 weight % of odium stearate；
4.4 weight % of sodium benzoate；79.1 weight % of lubricating base oil；S10.4 weight %；0.7 weight % of barium mahogany sulfonate.
Embodiment 7
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by 311 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 85.34 grams of stearic acid addition systems
In fat kettle, agitating and heating, is warming up to 90 DEG C at 300 rpm, and adding in the aqueous solution containing 10.26 grams of sodium hydroxides, (concentration is 18 weights
Measure %), 105 DEG C are warming up to, carries out saponification 2h, then 32.97 grams of benzoic acid are added in into system, carry out recombination reaction 2h；
(2) 110 DEG C are warming up to, adds in 292 grams of PAO6 synthetic hydrocarbon oils, is warming up to 220 DEG C, refines 15min；
(3) 266 grams of PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 80 DEG C, adds in 8 grams of S1,7 grams of barium mahogany sulfonates,
It is stirred evenly under 300rpm；
(4) 4 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：9.1 weight % of odium stearate；Benzene
3.8 weight % of sodium formate；85.6 weight % of lubricating base oil；S10.8 weight %；0.7 weight % of barium mahogany sulfonate.
Embodiment 8
The present embodiment is used to illustrate sodium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 285 grams of 500SN and 150BS, (100 DEG C of viscosity are 14mm2/ s, similarly hereinafter) and 113.79 grams of tristearin
Acid is added in fat kettle processed, the agitating and heating under 230rpm, is warming up to 85 DEG C, adds in the aqueous solution (concentration containing 32 grams of sodium hydroxides
For 12 weight %), 100 DEG C are warming up to, carries out saponification 3h, then 48.85 grams of benzoic acid are added in into system, it carries out compound anti-
Answer 3h；
(2) 120 DEG C are warming up to, adds in the miscella of 270 grams of 500SN and 150BS, is warming up to 210 DEG C, refines 20min；
(3) miscella of 253 grams of 500SN and 150BS is added in, stirring is cooled to 85 DEG C, adds in 6 grams of S1,7 grams of mahogany acids
Barium stirs evenly under 230rpm；
(4) 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：12.2 weight % of odium stearate；
5.8 weight % of sodium benzoate；80.7 weight % of lubricating base oil；S10.6 weight %；0.7 weight % of barium mahogany sulfonate.
Comparative example 2
Method according to embodiment 8 prepares sodium base grease, unlike, S1 is replaced with to the diphenylamines of equivalent.Product
Performance is as shown in table 2.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：12.2 weight % of odium stearate；
5.8 weight % of sodium benzoate；80.7 weight % of lubricating base oil；0.6 weight % of diphenylamines；0.7 weight % of barium mahogany sulfonate.
Table 1
Each indication test method：Dropping point：GB/T3498；Work cone penetration：GB/T269；Oxidation onset temperature：ASTM
D5483；Mechanical admixture：Acid decomposition；Copper corrosion：GB/T7326；Anticorrosive property：GB/T5018.
Table 2
Each indication test method：Dropping point：GB/T3498；Work cone penetration：GB/T269；Oxidation stability：SH/T0325；
Stencil oil-dividing：SH/T0324；Copper corrosion：GB/T7326；Anticorrosive property：GB/T5018.
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 onset temperature is higher, and the oxidation resistance of lubricating grease is better；Oxidation stability is smaller, and the antioxygenic property of lubricating grease is got over
It is good.
By embodiment 4 compared with comparative example 1, by embodiment 8 compared with comparative example 2, it can be seen that the present invention
Lubricating grease have better inoxidizability.
Lubricant composition provided by the invention has good colloid stability, more has on antioxygenic property apparent
Advantage, and have good compatibility with other lubricating grease.Enable the fat be competent in various motors, generator, air blower,
The lubrication of transportation, iron and steel enterprise and other various industrial equipments, especially suitable for the various ball bearings such as high speed, middling speed
Lubrication.
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 (17)
1. a kind of excellent sodium base grease composition of antioxygen property, on the basis of the weight of lubricant composition, the lubrication
Oil/fat composition includes following components：The lubricating base oil of 65-95 weight %, the sodium base thickening agent of 4-30 weight % and 0.1-15 weights
Measure the additive of %, 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 70-90 weight %, the sodium base thickening agent of 4-28 weight % and 1-10 weights
Measure the additive of %.
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 sodium base thickening agent is anti-with sodium hydroxide for acid
It should generate, the acid includes higher fatty acids and optional 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 1 or 2, wherein, the additive also contains antirust agent.
10. lubricant composition according to claim 9, wherein, the antirust agent is barium mahogany sulfonate, dinonyl benzene sulphur
At least one of sour barium and Lanolin Calcium Soap.
11. the preparation method of lubricant composition described in claim 1, the described method includes：
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, 70-90 DEG C is warming up to, adds in sodium hydroxide,
Saponification is carried out, then optionally, small molecule acid is added in and carries out recombination reaction；
(2) 100-120 DEG C is warming up to, adds in the lubricating base oil of 1/5-2/5,180-220 DEG C is warming up to and is refined；
(3) remaining lubricating base oil is added in, 80-100 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller.
12. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
The dosage for the sodium base thickening agent that dosage is prepared for 70-90 weight %, by higher fatty acids, optional small molecule acid and sodium hydroxide
For 4-28 weight %, the dosage of additive is 1-10 weight %.
13. the method according to claim 11 or 12, 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 %.
14. 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 %.
15. the method according to claim 11 or 12, wherein, the total amount and hydrogen of higher fatty acids and optional small molecule acid
The molar ratio of sodium oxide molybdena is stoichiometric ratio；The molar ratio of higher fatty acids and optional small molecule acid is 1:0.1-1.
16. the method according to claim 11 or 12, wherein, in step (1), saponification temperature is 100-110 DEG C, soap
The change reaction time is 1-3h, and optional complex reaction time is 1-3h.
17. the method according to claim 11 or 12, wherein, in step (2), the time of the refining is 5-20min.
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| CN114672360A (en) * | 2022-04-26 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature high-speed flexible gyroscope motor bearing lubricating grease and preparation method thereof |
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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 |
| CN102876427A (en) * | 2012-10-29 | 2013-01-16 | 郭小川 | Composite sodium-urea lubricating grease and preparation method thereof |
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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 |
| CN102876427A (en) * | 2012-10-29 | 2013-01-16 | 郭小川 | Composite sodium-urea lubricating grease and preparation method thereof |
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