CN105585536B - A kind of antioxidant and its preparation method and application - Google Patents
A kind of antioxidant and its preparation method and application Download PDFInfo
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- CN105585536B CN105585536B CN201410573320.6A CN201410573320A CN105585536B CN 105585536 B CN105585536 B CN 105585536B CN 201410573320 A CN201410573320 A CN 201410573320A CN 105585536 B CN105585536 B CN 105585536B
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Abstract
The invention discloses a kind of antioxidant, the antioxidant has the structure shown in formula (I).A kind of preparation method of antioxidant is also disclosed, is comprised the following steps：(1) 2,6 DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II)；(2) the intermediate M for obtaining step (1) is contacted with bromide reagent carries out bromo-reaction, generates the bromination product shown in formula (III)；(3) bromination product that step (2) obtains is made to be contacted with formula (IV) compound represented and carries out coupling reaction, generates the antioxidant shown in formula (I).Also disclose application of the antioxidant in lubricating grease, lubricating oil.The antioxidant of the present invention has excellent antioxidant capacity, and oil-soluble is good, has preferable compatibility, no special odor with other additives；Additive amount in lubricating oil, lubricating grease is 0.5 3 weight %, you can plays good result.
Description
Technical field
The present invention relates to a kind of antioxidant, the preparation method of the antioxidant and the antioxidant are in lubricating grease, lubricating oil
Application.
Background technology
Lubricating oil, lubricating grease are in use by many factors such as environment temperature, oxygen and catalytic action of metal ion
Influence, be oxidized easily rotten generation low molecular compound, further condensation is formed under polymer and the deposition of high molecular weight
Come.This oxidation not only promotes the formation of corrosive oxidation products and residue in oil, additionally it is possible to cause viscosity increase very
Cure to causing, product greasy property is made to be deteriorated, shorten the working life or even can corrosion of mechanical equipment.Therefore lubricating oil, lubrication
Fat inhibits this oxidation process to a certain extent usually using antioxidant in use, extends oily, fat make
With the service life, ensure that product quality is stablized.
The additive that can effectively play antioxidation is currently known mainly including phenols and aminated compounds.Phenol generalization
It closes object and contains one or more and be obstructed phenol functional group, aminated compounds is then containing one or more nitrogen-atoms, these special officials
Can group can capture the free radical compounds of oxidation process generation, so as to which oxidation process be prevented to continue to occur.Due to current machine
The operating condition of tool equipment tends to be strong, often accelerated oxidation rate, shortens the service life of grease, therefore to antioxidant
Efficiency and economy propose higher requirement.
United States Patent (USP) US4824601A reports the alkaline-earth metal catalyst of diphenylamine and diisobutylene in acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, it is in lubricating oil and other functional fluid moderate resistance energy of oxidations
Power performance is excellent.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of below general formula, the synthesis of 10- acridans
Method, it is condensed preparation using alkylated diphenylamine and aldehydes or ketones under acidic catalyst effect.
Patent CN1191340C occurs prepared by condensation using the tertiary butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine
Compound has the ability of stronger capture free radical and peroxynitrite decomposition compound, can be provided to oil oxidation stability more effective
Protection, may also function as wear-resistant effect.
Patent US4225450 reports a kind of by tertiary butyl phenols and the Diethyldithiocarbamate reaction preparation of being obstructed
Polysulfide phenolic antioxidant, have preferable antioxidation and wear-resistant effect.
In order to adapt to the operating condition of Current mechanical equipment, still need to research and development it is new there is excellent additive.
The content of the invention
The purpose of the invention is to adapt to the operating condition of Current mechanical equipment, providing a kind of new has the good oil molten
The preparation method and application of property, the antioxidant of antioxidant and the antioxidant.
On the one hand, the present invention provides a kind of antioxidant, the antioxidant has the structure shown in formula (I)：
Second aspect, the present invention provides a kind of preparation methods of antioxidant, the described method comprises the following steps：
(1) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II),
(2) the intermediate M for obtaining step (1) is contacted with bromide reagent carries out bromo-reaction, generates shown in formula (III)
Bromination product,
(3) bromination product that step (2) obtains is made to be contacted with formula (IV) compound represented and carries out coupling reaction, production
(I) antioxidant shown in,
Preferably, in step (1), the condition of the condensation reaction includes：Under an inert atmosphere, in the first solvent,
In the presence of first catalyst, risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted 0.5-1.5h at -20-0 DEG C
15-30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
Preferably, in step (2), the condition of the bromo-reaction includes：Under an inert atmosphere, in the second solvent,
In the presence of second catalyst, under the conditions of being protected from light, the intermediate M and bromide reagent that step (1) is obtained are anti-at 15-30 DEG C
1-2h is answered, is then quenched with quencher.
Preferably, in step (3), the condition of the coupling reaction includes：Under an inert atmosphere, in the 3rd solvent,
In the presence of 3rd catalyst, the bromination product and formula (IV) compound represented that step (2) is obtained are anti-at 80-100 DEG C
Answer 4-8h.
The third aspect, the present invention provides application of the antioxidant as described above in lubricating grease.
Fourth aspect, the present invention provides application of the antioxidant as described above in lubricating oil.
The antioxidant of the present invention has excellent antioxidant capacity, and oil-soluble is good, has preferable compatibility with other additives
Property, no special odor；Additive amount in lubricating oil, lubricating grease is 0.5-3 weight %, you can plays good result.The present invention
Antioxidant antioxidant and metal deactivator can be used as to be widely used in lubricating oil, lubricating grease field.
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 the method for the present invention step (1).
Fig. 2 is the reaction equation of the method for the present invention step (2).
Fig. 3 is the reaction equation of the method for the present invention step (3).
Fig. 4 is the hydrogen spectrum spectrogram of antioxidant prepared by embodiment 1.
Fig. 5 is the carbon spectrum spectrogram of antioxidant prepared by embodiment 1.
Fig. 6 is the mass spectrogram of antioxidant prepared by embodiment 1.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In a first aspect, the present invention provides a kind of antioxidant, which has the structure shown in formula (I)：
Second aspect, the present invention provides a kind of preparation method of antioxidant, this method comprises the following steps：
(1) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II),
(2) the intermediate M for obtaining step (1) is contacted with bromide reagent carries out bromo-reaction, generates shown in formula (III)
Bromination product,
(3) bromination product that step (2) obtains is made to be contacted with formula (IV) compound represented and carries out coupling reaction, production
(I) antioxidant shown in,
In step (1) 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 (1) 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 (1) 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 (1) 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 (2) 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, the intermediate M that step (1) obtains and bromide reagent are reacted 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 (2) 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 (2) 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 (2) 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 (2), 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 (2) 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 (2) 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 (3) 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 (2) 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 (3) of the present invention, bromination product and the dosage of formula (IV) compound represented that step (2) 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 (2) obtains
The molar ratio of compound be preferably 0.9-1.5:0.9-2.5.
In step (3) 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 (3) of the present invention, bromination product that step (2) 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 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 100-800rpm.
In the method for the present invention, for the first solvent, the second solvent and the 3rd solvent amount without particular/special requirement, can be ability
The solvent dosage of domain routine, this is known to those skilled in the art, and details are not described herein.
The third aspect, the present invention provides application of the antioxidant as described above in lubricating grease.
Fourth aspect, the present invention provides application of the antioxidant as described above in lubricating oil.
In the present invention, antioxidant of the invention can be used as antioxidant and metal deactivator to use in lubricating oil, lubricating grease.
In lubricating oil, lubricating grease, the dosage of antioxidant of the invention, can be according to the use of lubricating oil, lubricating grease without particular/special requirement
It needs to be determined that.Under normal circumstances, the additive amount of antioxidant of the invention in lubricating oil, lubricating grease is 0.5-3 weight %, you can
Play good antioxidant effect.
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.
Embodiment 1
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.
Embodiment 2
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 350rpm), adds in 200ml
Methanol and 0.04mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyls of 0.2mol
Phenol, the formaldehyde of 0.6mol and the benzene of 0.8mol.React 0.5 it is small when after remove ice-water bath, be heated to after rising to 15 DEG C 70 DEG C continue
Flow back 3 it is small when after stop reaction, the system after reaction is steamed into solvent at 0.01MPa, 40 DEG C, then add in 300ml dichloros
Methane, and being transferred in separatory funnel, respectively with 150ml distilled water (twice) and 75ml saturated common salt water washings, and add in 15g without
Aqueous sodium persulfate dry 60min, filtrate after filtering at 15 DEG C are evaporated off solvent under 50 DEG C, 0.05MPa, obtain midbody product
M1。
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 350rpm), adds in 200ml
Dry tetrahydrofuran, then dissolve in midbody product M1, and add in the BPO of 0.08mol, be slowly added under the conditions of being protected from light
0.3mol brominated reagents NBS.2h is stirred to react at 15 DEG C, is then quenched with saturated salt solution, then with 150ml distilled water
(twice) wash, and add in 15g anhydrous calcium chlorides dry 60min at 15 DEG C.Filtrate after filtering is under 50 DEG C, 0.05MPa
Solvent is evaporated off, obtains bromination product.
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 350rpm), adds in 150ml
Dichloromethane as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.28mol, then add in
The dinaphthol of 0.02mol, the potassium tert-butoxide of 0.02mol and the Pd of 0.016mol2(dba)3.80 DEG C are gradually heating to, it is lasting to stir
8h.Then the filtrate after the system filtering after reaction is added in into 300ml dichloromethane, and be transferred in separatory funnel, steamed with 150ml
Distilled water (twice) is washed, and adds in 15g anhydrous calcium chlorides dry 60min at 15 DEG C.Filtrate after filtering 50 DEG C,
Solvent is evaporated off under 0.05MPa, obtains final product S2.
The physico-chemical analysis data of S2 are as follows：Nitrogen content, 11.3%.
S2 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively with Fig. 4, Fig. 5 and
Fig. 6 is similar.
Embodiment 3
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 500rpm), adds in 120ml
Methanol and 0.015mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-t-butyls of 0.05mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.25mol.React 1.5 it is small when after remove ice-water bath, 80 DEG C are heated to after rising to 30 DEG C and is held
Stop reaction after when continuous reflux 1 is small, the system after reaction is steamed into solvent at 0.05MPa, 60 DEG C, then adds in 200ml second
Acetoacetic ester, and being transferred in separatory funnel respectively with 80ml distilled water (twice) and 40ml saturated common salt water washings, and adds in 10g
Solvent is evaporated off under 60 DEG C, 0.01MPa in anhydrous sodium sulfate dry 10min, filtrate after filtering at 30 DEG C, obtains intermediate production
Object M1.
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 500rpm), adds in 120ml
Dry tetrahydrofuran, then dissolve in midbody product M1, and add in the AIBN of 0.03mol, be slowly added under the conditions of being protected from light
0.125mol brominated reagents NBS.1h is stirred to react at 30 DEG C, is then quenched with saturated salt solution, then with 80ml distilled water
(twice) wash, and add in 10g anhydrous sodium sulfates dry 10min at 30 DEG C.Filtrate after filtering is under 60 DEG C, 0.01MPa
Solvent is evaporated off, obtains bromination product.
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 500rpm), adds in 120ml
Dichloromethane as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.08mol, then add in
The cesium carbonate of the dppf of 0.008mol, 0.005mol and the Pd (OAc) of 0.004mol2.100 DEG C are gradually heating to, it is lasting to stir
4h.Then the filtrate after the system filtering after reaction is added in into 200ml dichloromethane, and be transferred in separatory funnel, steamed with 80ml
Distilled water (twice) is washed, and adds in 10g anhydrous sodium sulfates dry 10min at 30 DEG C.Filtrate after filtering 60 DEG C,
Solvent is evaporated off under 0.01MPa, obtains final product S3.
The physico-chemical analysis data of S3 are as follows：Nitrogen content, 11.2%.
S3 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively with Fig. 4, Fig. 5 and
Fig. 6 is similar.
Physico-chemical analysis data, Fig. 4, Fig. 5 and Fig. 6 from above-described embodiment can be seen that the antioxygen of the method for the present invention preparation
Agent has the structure shown in formula (I).
Test example
By 540kg500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) with the 12- hydroxy stearic acids of 37.95kg and
23.77kg azelaic acids are added in fat kettle processed, and then stirring is warming up to 85 DEG C and adds in lithium hydroxide aqueous solution (wherein containing lithium hydroxide
16.39kg, water 20kg) reaction 0.5h is carried out, then be warming up to 200 DEG C and carry out high temperature refining 5min；Add in 180kg500SN bases
After oil cools to 120 DEG C, 16kg S1 are added in, are stirred evenly；It is ground 2 times by three-roller and obtains lubricating grease A1.
In lubricating grease A1, on the basis of lubricating grease weight, form and be：4.8 weight % of 12- hydroxy lithium stearates；Azelaic acid
3.2 weight % of lithium；90 weight % of lubricating base oil；S12 weight %.
Above-mentioned preparation process is repeated, unlike, S1 is replaced with into di-iso-octyldiphenylamine (Vanlube81), is moistened
Consistent lubricant A2.
The properties of product of A1, A2 are as shown in table 1.
Table 1
It will be understood by those skilled in the art that pressure drop values are smaller, the antioxygenic property of lubricating grease is better；It aoxidizes
Beginning temperature is higher, and the oxidation resistance of lubricating grease is better；Oxidation induction period is longer, and the antioxygenic property of lubricating grease is better.
Therefore, as it can be seen from table 1 the antioxidant of the present invention is added in lubricating grease, can have lubricating grease excellent
Antioxygen property.
The antioxidant of the present invention has excellent antioxidant capacity, and oil-soluble is good, has preferable compatibility with other additives
Property, no special odor；Additive amount in lubricating oil, lubricating grease is 0.5-3 weight %, you can plays good result.The present invention
Antioxidant antioxidant and metal deactivator can be used as to be widely used in lubricating oil, lubricating grease field.
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 (33)
1. a kind of antioxidant, which is characterized in that the antioxidant has the structure shown in formula (I)：
2. a kind of preparation method of antioxidant, which is characterized in that the described method comprises the following steps：
(1) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II),
(2) the intermediate M for obtaining step (1) is contacted with bromide reagent carries out bromo-reaction, generates the bromo shown in formula (III)
Product,
(3) bromination product that step (2) obtains is made to be contacted with formula (IV) compound represented and carries out coupling reaction, generates formula (I)
Shown antioxidant,
3. according to the method described in claim 2, wherein, in step (1), the condition of the condensation reaction includes：In indifferent gas
Under atmosphere, in the first solvent, in the presence of the first catalyst, by 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene at -20-0 DEG C
15-30 DEG C is risen to after reaction 0.5-1.5h, is then heated to 70-80 DEG C of reaction 1-3h.
4. according to the method described in claim 3, wherein, first solvent is selected from methanol, ethyl alcohol, n,N-Dimethylformamide
At least one of with acetonitrile.
5. according to the method described in claim 4, wherein, first solvent is methanol and/or acetonitrile.
6. according to the method described in claim 5, wherein, first solvent is methanol.
7. according to the method described in claim 3, wherein, first catalyst is selected from acetic acid, p-methylbenzoic acid and benzene sulphur
At least one of acid.
8. according to the method described in claim 7, wherein, first catalyst is acetic acid.
9. according to the method in claim 2 or 3, wherein, the molar ratio of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is 0.9-
1.5:0.9-10:0.9-10。
10. according to the method described in claim 3, wherein, on the basis of the molal quantity of 2,6- DI-tert-butylphenol compounds, described first
The dosage of catalyst is 5-100 moles of %.
11. according to the method described in claim 10, wherein, on the basis of the molal quantity of 2,6- DI-tert-butylphenol compounds, described
The dosage of one catalyst is 10-30 moles of %.
12. according to the method described in claim 2, wherein, in step (2), the condition of the bromo-reaction includes：In indifferent gas
Under atmosphere, in the second solvent, in the presence of the second catalyst, under the conditions of being protected from light, intermediate M that step (1) is obtained with
Bromide reagent reacts 1-2h at 15-30 DEG C, is then quenched with quencher.
13. according to the method for claim 12, wherein, second solvent be selected from tetrahydrofuran, dichloromethane, chloroform and
At least one of ether.
14. according to the method for claim 13, wherein, second solvent is tetrahydrofuran.
15. according to the method for claim 12, wherein, second catalyst be selected from ammonium nitrate, benzoyl peroxide and
At least one of azodiisobutyronitrile.
16. the method according to claim 2 or 12, wherein, the bromide reagent for N-bromosuccinimide and/or
Br2。
17. according to the method for claim 16, wherein, the bromide reagent is N-bromosuccinimide.
18. the method according to claim 2 or 12, wherein, the molar ratio of the intermediate M and the bromide reagent are
0.9-1.2:0.9-3.0。
19. the method according to claim 11, wherein, on the basis of the molal quantity of intermediate M, second catalyst
Dosage is 10-100 moles of %.
20. the method according to claim 11, wherein, on the basis of the molal quantity of intermediate M, second catalyst
Dosage is 40-60 moles of %.
21. according to the method described in claim 2, wherein, in step (3), the condition of the coupling reaction includes：In indifferent gas
Under atmosphere, in the 3rd solvent, in the presence of the 3rd catalyst, bromination product that step (2) is obtained with shown in formula (IV)
Compound reacts 4-8h at 80-100 DEG C.
22. according to the method for claim 21, wherein, the 3rd solvent is selected from dichloromethane, chloroform, toluene and tetrahydrochysene
At least one of furans.
23. according to the method for claim 22, wherein, the 3rd solvent is dichloromethane.
24. according to the method for claim 21, wherein, the 3rd catalyst is palladium salt, ligand and alkali.
25. according to the method for claim 24, wherein, the palladium salt is selected from palladium and/or palladium-dibenzalacetone network
Close object.
26. according to the method for claim 24, wherein, the ligand is selected from tri-tert phosphorus, dinaphthol and double (diphenyl
At least one of phosphino-) ferrocene.
27. according to the method for claim 24, wherein, the alkali is selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and carbonic acid
At least one of sodium.
28. the method according to claim 2 or 21, wherein, the bromination product that step (2) obtains and the change shown in formula (IV)
The molar ratio for closing object is 0.9-1.5:0.9-2.5.
29. the method according to claim 11, wherein, on the basis of the molal quantity of bromination product, the dosage of the palladium salt
For 5-50 moles of %；The dosage of the ligand is 5-50 moles of %；The dosage of the alkali is 5-50 moles of %.
30. the method according to claim 11, wherein, on the basis of the molal quantity of bromination product, the dosage of the palladium salt
For 5-20 moles of %；The dosage of the ligand is 10-30 moles of %；The dosage of the alkali is 10-30 moles of %.
31. the method according to claim 11, wherein, on the basis of the molal quantity of bromination product, the dosage of the palladium salt
For 5-10 moles of %.
32. application of the antioxidant described in claim 1 in lubricating grease.
33. application of the antioxidant described in claim 1 in lubricating oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of benzotriazole derivatives as antioxidants industrial lubricating oils;El-Ashry等;《Lubrication Science》;20060410;第18卷(第2期);109-118 * |
| 润滑油抗氧剂的研究现状与进展;薛卫国等;《合成润滑材料》;20130620;第40卷(第2期);7-12 * |
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