CN105586132B - Excellent bentonite grease composition of a kind of antioxygenic property and preparation method thereof - Google Patents
Excellent bentonite grease composition of a kind of antioxygenic property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the bentonite grease composition that a kind of antioxygenic property is excellent, and on the basis of the weight of lubricant composition, the lubricant composition includes following components：The additive of 65 95 weight % lubricating base oil, 5 35 weight % bentonite thickening agent and 0.1 15 weight %, the additive contain the compound of structure shown in formula (I).Present invention also offers the preparation method of the excellent bentonite grease composition of antioxygenic property.Oxidation resistance of the lubricant composition of the present invention due to containing specific antioxidant, drastically increasing lubricating grease.The lubricating grease of the present invention has splendid inoxidizability, colloid stability and water proofing property etc., can be competent in the harsh working conditions such as high temperature, high speed, high load capacity, more water.
Description
Technical field
The present invention relates to lubricating grease field, in particular it relates to which a kind of antioxygenic property containing special additive is excellent
Bentonite grease composition and preparation method thereof.
Background technology
Bentonite grease is a kind of important nonsoap grease prepared with modified alta-mud multigrade oil.Swelling
Native lubricating grease not only has good heat resistance, while has good mechanical stability and colloid stability, heat-resisting bentonite
Lubricating grease and extreme-pressure bentonite grease lubricant be widely used in metallurgical equipment, casting and steel rolling equipment, mine heavy duty equipment,
Large-scale truck, papermaking equipment, cement manufacture plant, high temp tunnel cellar car, airplane wheel bearing, railway diesel locomotive, pipe
The lubrication of the equipment such as formula thread seal sub-assembly.
Smith in 1934 has carried out pioneering research to the exchange reaction of sodium bentonite and organoammonium ions, and synthesizes
Some organobentonites.Jorda in 1949 thinks that different alkyl have large effect to montmorillonite construction interlamellar spacing.In recent years very
More patents have inquired into formula, production technology and the performance of bentonite grease.CN1504552 uses oil based on vegetable oil, amine
Class or amine and phenols mixing antioxidant, are prepared for a kind of biodegradable lubricating grease, meet environmental requirement；CN1197107
Using oil based on polyalphaolefin, phenyl-β-naphthylamine and di-iso-octyldiphenylamine are antioxidant and add antirust agent, extreme pressure agent, divide
Powder is prepared for a kind of aviation bentonite grease, and the fat has the compatibility of good high and low temperature and rubber parts and dashed forward
The antioxidant that goes out, extreme pressure property；CN101886017 is prepared for a kind of bentonite grease using furfural refining oil, and the fat is additionally added
Antioxidant and pigment, make the bentonite grease that there is good oxidation stability and corrosion resistance, and pigment plus
The function of assigning product particular appearance and auxiliary difference lubricating grease species can be played by entering；CN101240208 passes through to technique
Improve, the selection to antirust agent so that obtained bentonite grease has on thickening ability and rustless property very big to be entered
Step, water repelling property is also improved, but is not directed to antioxygenic property.
The life-span of lubricating grease can shorten with temperature in use rising or the extension of lubrication time.Chemically say, make in nature
Metal soap for thickening agent is the major reason for causing lubricating grease oxidation deterioration.In order to suppress the oxidation deterioration of lubricating grease, prevent
Oxidation product causes the corrosion of metal surface, to add appropriate antioxidant additive.At present, conventional antioxidant mainly divides
For amine and the class of phenols two.Phenolic antioxidant generally comprises BHT, 2,6- di-tert-butylphenols etc., but it makes
It is relatively low with temperature, typically within 150 DEG C.Amine antioxidants are mainly alkylated diphenylamine etc..
The content of the invention
The invention aims to meet the high request to the antioxygenic property of lubricating grease, there is provided a kind of antioxygenic property
Excellent bentonite grease composition.
The present inventor has found that the additive in lubricant composition contains structure shown in formula (I) under study for action
Antioxidant：
It can make lubricant composition that there is the excellent performance such as anti-oxidant.
Therefore, to achieve these goals, on the one hand, the invention provides the bentonite profit that a kind of antioxygenic property is excellent
Grease composition, on the basis of the weight of lubricant composition, the lubricant composition includes following components：65-95 weights
% lubricating base oil, 5-35 weight % bentonite thickening agent and 0.1-15 weight % additive is measured, the additive contains
There is the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the lubricant composition includes following components：80-94
The additive of weight % lubricating base oil, 5-15 weight % bentonite thickening agent and 1-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the content of the compound of structure shown in formula (I) is 0.1-3
Weight %, more preferably 0.2-1 weight %.
On the other hand, the invention provides a kind of preparation side of the excellent bentonite grease composition of antioxygenic property
Method, methods described include：
(1) 1/2-2/3 lubricating base oil and antioxidant are added in fat kettle processed, are well mixed；
(2) bentonite thickening agent is added, is well mixed；
(3) dispersant is added, and is quickly stirred, until forming grease structure in kettle；
(4) 50-65 DEG C of holding 5-20min is warming up to, remaining base oil, other additives is added, is well mixed；
(5) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, bentonite
The dosage of thickening agent is 5-35 weight %, and the dosage of dispersant is 2-10 weight %, and the dosage of additive is 0.1-15 weight %,
The antioxidant 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 80-94 weight %, swelling
The dosage of native thickening agent is 5-15 weight %, and the dosage of additive is 1-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the dosage of the compound of structure shown in formula (I) is 0.1-3
Weight %, more preferably 0.2-1 weight %.
Anti-oxidant energy of the lubricant composition of the present invention due to containing specific antioxidant, drastically increasing lubricating grease
Power.The present invention lubricating grease there is splendid inoxidizability, colloid stability and water proofing property etc., can be competent in high temperature, high speed,
The harsh working conditions such as high load capacity, more water.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing antioxidant.
Fig. 2 is the reaction equation of (b) the step of preparing antioxidant.
Fig. 3 is the reaction equation of (c) the step of preparing antioxidant.
Fig. 4 is the hydrogen spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 5 is the carbon spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 6 is the mass spectrogram of antioxidant prepared by preparation example.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides the bentonite grease composition that a kind of antioxygenic property is excellent, with the weight of lubricant composition
On the basis of amount, lubricant composition includes following components：65-95 weight % lubricating base oil, 5-35 weight % bentonite
The additive of 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 80-94 weight % lubricating base oil, 5-15 weight % bentonite thickening agent and 1-10 weight %.
In the present invention, on the basis of the weight of lubricant composition, the content of the compound of structure is preferably shown in formula (I)
0.1-3 weight %, more preferably 0.2-1 weight %.
It is contemplated that by the additive in bentonite grease composition contain the compound of structure shown in formula (I) and
Goal of the invention is realized, even if bentonite grease composition has the excellent performance such as anti-oxidant.Therefore, lubricated for bentonite
The selection of each conventional constituents, is not limited specifically in fat.
In the present invention, lubricating base oil can be lubricating base oil commonly used in the art, for example, can be mineral oil,
At least one of vegetable oil and artificial oil.100 DEG C of kinematic viscosity of lubricating base oil are preferably 5-50mm2/ s, more preferably 6-
28mm2/s.For the specific species of mineral oil, vegetable oil and artificial oil, also there is no particular limitation, and this area can be used normal
Mineral oil, vegetable oil and artificial oil, for example, mineral oil can select paraffinic base, cycloalkyl, intermediate base series, vegetable oil
Can be at least one of castor oil, rapeseed oil, peanut oil and soybean oil etc., artificial oil can be poly-a-olefin oil (PAO),
At least one of Esters oil, fluorocarbon oil and ether system artificial oil etc..
In the present invention, bentonite thickening agent is preferably organobentonite.
In the present invention, because the antioxidant of structure shown in formula (I) and other additives have preferable compatibility, therefore,
According to the use needs of lubricating grease, additive of the invention can also contain other extreme pressure anti-wear additives and/or antirust agent.
In the present invention, for other extreme pressure anti-wear additives, antirust agent species and content without particular/special requirement, this can be used
The conventional species and content in field.For example, extreme pressure anti-wear additives can be two thio Acidic phosphates zinc, two thio dialkyl amidos
Formic acid molybdenum, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), dibutyl dithiocaarbamate antimony, two sulphur
Change at least one of tungsten, selenium disulfide, fluorographite, calcium carbonate and zinc oxide, the content of extreme pressure anti-wear additives can account for lubrication
The 0.5-12 weight % of oil/fat composition gross weight, preferably 0.5-5 weight %；Antirust agent can be barium mahogany sulfonate, oil sulphur
At least one of sour sodium, benzothiazole, BTA, decanedioic acid sodium, zinc naphthenate and alkenyl succinic acid, antirust agent contains
Amount can account for the 0.01-4.5 weight %, preferably 0.1-2 weight % of lubricant composition gross weight.
In the present invention, the preparation method of the compound of structure preferably includes shown in formula (I)：
(a) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate the intermediate M shown in formula (II),
(b) the intermediate M that step (a) obtains is contacted with bromide reagent and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product that step (b) obtains is contacted with the compound shown in formula (IV) and carry out coupling reaction, production
(I) antioxidant shown in,
In step (a) of the present invention, the condition of condensation reaction preferably includes：Under an inert atmosphere, in the first solvent,
In the presence of one catalyst, 15- is risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted into 0.5-1.5h at -20-0 DEG C
30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, such as can be by gases such as nitrogen, argon gas
There is provided.
It will be understood by those skilled in the art that in order that stable reaction progress, reacts 0.5-1.5h at -20-0 DEG C
After rise to 15-30 DEG C, it should be to slowly warm up to 15-30 DEG C, for example, can by -20-0 DEG C react 0.5-1.5h after body
System is placed under 15-30 DEG C of environment temperature, reaction system itself is to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethanol, DMF and acetonitrile
Kind, more preferably methanol and/or acetonitrile, are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, p-methylbenzoic acid and benzene
At least one of sulfonic acid, more preferably acetic acid.
In the present invention, the dosage of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but formaldehyde and benzene can
With appropriate excessive.The mol ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably 0.9-1.5:0.9-10:0.9-10.
In step (a) of the present invention, the dosage of the first catalyst can be catalytic amount, with mole of 2,6- DI-tert-butylphenol compounds
On the basis of number, the dosage of the first catalyst is preferably 5-100 moles of %, more preferably 10-30 moles of %.
It will be understood by those skilled in the art that in step (a) of the present invention, in order to obtain purer intermediate M, also
Needing to post-process reacted system, the mode of post processing can include removal of solvent under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, reacted system is removed into solvent at 0.01-0.05MPa, 40-60 DEG C,
It is subsequently poured into the ethyl acetate (or dichloromethane) of 1-10 times of volume, respectively with distilled water and saturated common salt water washing, then
The drier such as anhydrous calcium chloride or anhydrous sodium sulfate is added at 15-30 DEG C, keeps 10-60min.It is filtered to remove drier
Afterwards, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction equation of condensation reaction as schemed
Shown in 1, in Fig. 1, the first solvent is using methanol, and the first catalyst is using acetic acid, purpose by way of example only, no
The scope of the present invention is construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction preferably includes：Under an inert atmosphere, in the second solvent,
In the presence of two catalyst, under the conditions of lucifuge, intermediate M that step (a) obtains is reacted at 15-30 DEG C with bromide reagent
1-2h, then it is quenched with quencher.
" inert atmosphere " is as it was previously stated, will not be repeated here.
It will be understood by those skilled in the art that more stably being carried out to react, slowly add preferably into intermediate M
Enter brominated reagent.
In the present invention, the second solvent is preferably selected from least one of tetrahydrofuran, dichloromethane, chloroform and ether, more
Preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azodiisobutyronitrile
At least one of (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more preferably NBS.
In step (b) of the present invention, it is quenched with quencher, quencher can be quencher commonly used in the art, such as
It can be saturated aqueous common salt.
In step (b) of the present invention, the dosage of intermediate M and bromide reagent is substantially equimolar amounts, but bromide reagent one
As can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate.Intermediate M and bromide reagent mol ratio are preferably 0.9-
1.2:0.9-3.0。
In step (b) of the present invention, the dosage of the second catalyst can be catalytic amount, on the basis of intermediate M molal quantity,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the inventive method step (b), intermediate M contacts the reaction equation for carrying out bromo-reaction with bromide reagent as schemed
Shown in 2, in Fig. 2, bromide reagent purpose by way of example only, is not construed as limiting using NBS to the scope of the present invention.
In step (b) of the present invention, in addition to the bromination product shown in generation formula (III), the bromo production at also micro ortho position
Thing generates, and is generated without the bromination product of meta, but the amount of the bromination product at ortho position very pettiness, does not have substantive shadow to subsequent reactions
Ring, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, in order to obtain purer bromination product,
Also need to post-process the system after being quenched, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, example
Such as, the system distillation water washing after being quenched, it is dry then to add anhydrous calcium chloride or anhydrous sodium sulfate etc. at 15-30 DEG C
Drying prescription, keep 10-60min.After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromine
For product.
In step (c) of the present invention, the condition of coupling reaction preferably includes：Under an inert atmosphere, in the 3rd solvent,
In the presence of three catalyst, the bromination product that step (b) obtains and the compound shown in formula (IV) are reacted at 80-100 DEG C
4-8h。
" inert atmosphere " is as it was previously stated, will not be repeated here.
In the present invention, in order that stable reaction is carried out, 80-100 DEG C is preferably gradually heating to, it is then anti-at 80-100 DEG C
Answer 4-8h.
In the present invention, the 3rd solvent is preferably selected from least one of dichloromethane, chloroform, toluene and tetrahydrofuran, more
Preferably dichloromethane.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali.Palladium salt is preferably selected from palladium and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3]；Part is preferably selected from tri-tert phosphorus, dinaphthol (BINAP) and double (diphenylphosphines
At least one of base) ferrocene (dppf)；Alkali is preferably selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate extremely
Few one kind.
In step (c) of the present invention, the dosage for the compound shown in bromination product and formula (IV) that step (b) obtains is substantially
For equimolar amounts, but the compound shown in formula (IV) can be suitably excessive.Shown in the bromination product and formula (IV) that step (b) obtains
The mol ratio of compound be preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the dosage of catalyst can be catalytic amount, on the basis of the molal quantity of bromination product, palladium
The dosage of salt is preferably 5-50 moles of %, more preferably 5-20 moles of %, is still more preferably 5-10 moles of %；The use of part
Amount is preferably 5-50 moles of %, more preferably 10-30 moles of %；The dosage of alkali is preferably 5-50 moles of %, more preferably 10-30
Mole %.
In step (c) of the present invention, bromination product that step (b) obtains contacts with the compound shown in formula (IV) to be coupled
The reaction equation of reaction is as shown in figure 3, in Fig. 3, and palladium salt is using palladium, purpose by way of example only, not to this
The scope of invention is construed as limiting.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e. antioxygen shown in formula (I)
Agent, the inventive method preferably also include post-processing reacted system, and the mode of post processing can include filtering, solvent
Dilution, washing, dry, removal of solvent under reduced pressure, for example, the filtrate after reacted system is filtered pours into the second of 1-10 times of volume
In acetoacetic ester (or dichloromethane), then with distillation water washing, anhydrous calcium chloride or anhydrous sulphur are then added at 15-30 DEG C
The drier such as sour sodium, keep 10-60min.After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C,
To obtain the antioxidant shown in formula (I).
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention is preferably carried out under agitation, for
Mixing speed can be the conventional mixing speed in this area, for example, mixing speed can be 100-800rpm without particular/special requirement.
The present invention is prepared in the method for the compound of structure shown in formula (I), molten for the first solvent, the second solvent and the 3rd
The amount of agent can be the conventional solvent load in this area, this is known to those skilled in the art, herein no longer without particular/special requirement
Repeat.
As described above, it is contemplated that structure shown in formula (I) is contained by the additive in bentonite grease composition
Compound and realize goal of the invention, even if lubricant composition has the excellent performance such as anti-oxidant.Therefore, for bentonite
Preparation of greases method can use method commonly used in the art, for example, second aspect, the present invention without particular/special requirement
A kind of preparation method of the excellent bentonite grease composition of antioxygenic property is additionally provided, methods described includes：
(1) 1/2-2/3 lubricating base oil and antioxidant are added in fat kettle processed, are well mixed；
(2) bentonite thickening agent is added, is well mixed；
(3) dispersant is added, and is quickly stirred, until forming grease structure in kettle；
(4) 50-65 DEG C of holding 5-20min is warming up to, remaining base oil, other additives is added, is well mixed；
(5) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, bentonite
The dosage of thickening agent is 5-35 weight %, and the dosage of dispersant is 2-10 weight %, and the dosage of additive is 0.1-15 weight %,
Characterized in that, the antioxidant contains the compound of structure shown in formula (I)：
In the present invention, the excellent bentonite grease composition of antioxygenic property can also be prepared with the following method, wrapped
Include：1/2-2/3 lubricating base oil and bentonite thickening agent are added in fat kettle processed, are well mixed；Dispersant is added, and quickly
Stirring, until forming grease structure in kettle；50-65 DEG C of holding 5-20min is warming up to, adds remaining base oil and additive
(including antioxidant), it is well mixed；Ground 2-3 times by three-roller.
In the inventive method, 1/2-2/3 lubricating base oil refers to the 1/2-2/3 for accounting for lubricating base oil total amount.
In the inventive method, for well mixed mode without particular/special requirement, various sides commonly used in the art can be used
Formula, for example, can stir by mixing, the speed of stirring for example can be 20-400rpm.
In the inventive method step (2), in order that mixing is more uniform, bentonite thickening agent is preferably slowly added to.
In the inventive method step (3), dispersant is added, and is quickly stirred, until forming grease structure in kettle.Quickly
It is 80-400rpm that stirring, which refers generally to mixing speed, and 5-30min is stirred in 80-400rpm, you can makes to form lubricating grease knot in kettle
Structure.
In the inventive method, dispersant can use dispersant commonly used in the art, such as can be acetone or carbonic acid third
Alkene ester.
It will be understood by those skilled in the art that when dispersant uses acetone, because the boiling point of acetone is relatively low, Yi Hui
Hair, therefore, during the heating of step (4) is kept, acetone vapors away, in the bentonite grease composition being prepared
In, do not contain acetone.Even if dispersant uses propene carbonate, the boiling point of propene carbonate is higher, can be retained in and be prepared
Bentonite grease composition in, therefore, will not be to the bentonite grease that is prepared but because the amount of dispersant is seldom
The performance of composition produces any influence.
In the present invention, " until forming grease structure in kettle ", in practical operation, to be formed with the change of denseness to judge
Grease structure, it was observed that denseness increases, that is, show to form grease structure in kettle, therefore, quick stirring is until denseness increases
Greatly.
In the inventive method, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 80-
94 weight %, the dosage of bentonite thickening agent are 5-15 weight %, and the dosage of additive is 1-10 weight %.
In the inventive method, on the basis of the weight of lubricant composition, the dosage of the compound of structure is excellent shown in formula (I)
Elect 0.1-3 weight %, more preferably 0.2-1 weight % as.
Lubricating base oil, bentonite thickening agent, additive are as it was previously stated, will not be repeated here.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
The physico-chemical analysis method of product：Constituent content is determined by inductively coupled plasma ion emission spectroscopy method.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Methanol and 0.01mol acetic acid, after sufficiently cool in ice-water bath, be then respectively adding 0.1mol 2,6- di-tert-butyls
Phenol, 0.2mol formaldehyde and 0.3mol benzene.Reaction removes ice-water bath after 1 hour, and 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Stream stops reaction after 2 hours, reacted system is steamed into solvent at 0.03MPa, 50 DEG C, then adds 250ml acetic acid second
Ester, and being transferred in separatory funnel, respectively with 100ml distilled water (twice) and 50ml saturated common salt water washings, and it is anhydrous to add 10g
Calcium chloride dries 20min at 25 DEG C, and the filtrate after filtering is evaporated off solvent under 40 DEG C, 0.03MPa, obtains midbody product
M1。
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Dry tetrahydrofuran, then dissolve in midbody product M1, and add 0.05mol ammonium nitrate, under the conditions of lucifuge slowly plus
Enter 0.1mol brominated reagents NBS.Stirring reaction 1.5h, is then quenched with saturated aqueous common salt at 25 DEG C, is then distilled with 100ml
Water (twice) washs, and adds 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds 150ml
Dichloromethane as solvent, be separately added into the benzotriazole compound of above-mentioned bromination product and 0.12mol, then add
0.02mol tri-tert phosphorus, 0.02mol sodium tert-butoxide and 0.005mol Pd (OAc)2.90 DEG C are gradually heating to, is continued
Stir 6h.Then the filtrate after reacted system is filtered adds 250ml ethyl acetate, and is transferred in separatory funnel, uses
100ml distilled water (twice) washs, and adds 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
S1 physico-chemical analysis data are as follows：Nitrogen content, 11.2%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 4, Fig. 5 and
Fig. 6.
Physico-chemical analysis data, Fig. 4, Fig. 5 and Fig. 6 from above-mentioned preparation example, which can be seen that S1, has knot shown in formula (I)
Structure.
Embodiment 1
The present embodiment is used to illustrate bentonite grease composition of the present invention and preparation method thereof.
By 50 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 6mm2/ s, similarly hereinafter) added with 0.8 gram of S1 in fat kettle processed,
It is uniformly mixed under 100rpm；7.22 grams of organobentonites (being purchased from Zhejiang Feng Hong, similarly hereinafter) are slowly added to thereto, and stirring is mixed
Close uniform；1.12 grams of acetone are added, 30min is stirred under 120rpm, until denseness increases；50 DEG C are warming up to, keeps 20min；
Remaining base oil, 2.4 grams of dialkyl dithiocarbamates, 0.16 gram of BTA, 0.64 gram of decanedioic acid sodium are added,
Stir；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：The weight % of S1 0.81, organic bentonite
Moisten soil 7.3 weight %, the weight % of base oil 88.65, the weight % of dialkyl dithiocarbamate 2.43, BTA
0.16 weight %, the weight % of decanedioic acid sodium 0.65.
Embodiment 2
The present embodiment is used to illustrate bentonite grease composition of the present invention and preparation method thereof.
By 55 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) added with 0.8 gram of S1 in fat kettle processed,
It is uniformly mixed under 150rpm；7.87 grams of organobentonites are slowly added to thereto, are uniformly mixed；Add 4.72 gram third
Ketone, 20min is stirred at 200 rpm, until denseness increases；65 DEG C are warming up to, keeps 10min；Add remaining base oil and 2.4
Gram dialkyl dithiocarbamate, 0.16 gram of BTA, 0.64 gram of decanedioic acid sodium, stir；Pass through three-roller
3 times are ground into fat.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：The weight % of S1 0.86, organic bentonite
Moisten soil 8.44 weight %, the weight % of base oil 87.27, the weight % of dialkyl dithiocarbamate 2.57, BTA
0.17 weight %, the weight % of decanedioic acid sodium 0.69.
Embodiment 3
The present embodiment is used to illustrate bentonite grease composition of the present invention and preparation method thereof.
By 35 grams of PAO10 synthetic hydrocarbon oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) added with 0.8 gram of S1 in fat kettle processed,
It is uniformly mixed under 130rpm；6 grams of organobentonites are slowly added to thereto, are uniformly mixed；4.25 grams of acetone are added,
25min is stirred under 150rpm, until denseness increases；55 DEG C are warming up to, keeps 20min；Add remaining base oil and 2.4 gram two
Diethyldithiocarbamate, 0.16 gram of BTA, 0.64 gram of decanedioic acid sodium, stir；2 are ground by three-roller
It is secondary into fat.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：The weight % of S1 0.84, organic bentonite
Moisten soil 6.27 weight %, the weight % of base oil 89.54, the weight % of dialkyl dithiocarbamate 2.51, BTA
0.17 weight %, the weight % of decanedioic acid sodium 0.67.
Embodiment 4
The present embodiment is used to illustrate bentonite grease composition of the present invention and preparation method thereof.
By 40 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and with 0.8 gram of S1 add in fat kettle processed,
It is uniformly mixed under 140rpm；5.5 grams of organobentonites are slowly added to thereto, are uniformly mixed；Add 2.93 gram third
Ketone, 30min is stirred under 180rpm, until denseness increases；60 DEG C are warming up to, keeps 12min；Add remaining base oil, 2.4 grams
Dialkyl dithiocarbamate, 0.16 gram of BTA, 0.64 gram of decanedioic acid sodium, stir；Ground by three-roller
3 times are ground into fat.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：The weight % of S1 0.82, organic bentonite
Moisten soil 5.67 weight %, the weight % of base oil 90.22, the weight % of dialkyl dithiocarbamate 2.47, BTA
0.16 weight %, the weight % of decanedioic acid sodium 0.66.
Comparative example 1
Method according to embodiment 4 prepares bentonite grease, unlike, S1 is replaced with to the diphenylamines of equivalent.Production
Moral character can be as shown in table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight % of diphenylamines 0.82, has
The weight % of machine bentonite 5.67, the weight % of base oil 90.22, the weight % of dialkyl dithiocarbamate 2.47, benzo three
The weight % of nitrogen azoles 0.16, the weight % of decanedioic acid sodium 0.66.
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；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018；Water drenches number of dropouts：SH/T
0109。
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 more preferable inoxidizability,
Colloid stability and water proofing property.
Anti-oxidant energy of the lubricant composition of the present invention due to containing specific antioxidant, drastically increasing lubricating grease
Power.The present invention lubricating grease there is splendid inoxidizability, colloid stability and water proofing property etc., can be competent in high temperature, high speed,
The harsh working conditions such as high load capacity, more water.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of excellent bentonite grease composition of antioxygenic property, described on the basis of the weight of lubricant composition
Lubricant composition includes following components：65-95 weight % lubricating base oil, 5-35 weight % bentonite thickening agent and
0.1-15 weight % additive, it is characterised in that the additive contains the compound of structure shown in formula (I)：
2. lubricant composition according to claim 1, wherein, on the basis of the weight of lubricant composition, the profit
Grease composition includes following components：80-94 weight % lubricating base oil, 5-15 weight % bentonite thickening agent and 1-10
Weight % additive.
3. lubricant composition according to claim 1 or 2, wherein, on the basis of the weight of lubricant composition, formula
(I) content of the compound of structure shown in is 0.1-3 weight %.
4. lubricant composition according to claim 3, wherein, on the basis of the weight of lubricant composition, formula (I) institute
The content for showing the compound of structure is 0.2-1 weight %.
5. lubricant composition according to claim 1 or 2, wherein, the lubricating base oil be mineral oil, vegetable oil and
At least one of artificial oil.
6. lubricant composition according to claim 1 or 2, wherein, the bentonite thickening agent is organobentonite.
7. lubricant composition according to claim 1 or 2, wherein, the additive also contains other extreme-pressure anti-wears
Agent and/or antirust agent.
8. lubricant composition according to claim 7, wherein, the extreme pressure anti-wear additives are two thio Acidic phosphates
Zinc, two thio dialkyl amido formic acid molybdenums, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), dibutyl two
At least one of thiocarbamic acid antimony, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide.
9. lubricant composition according to claim 7, wherein, the antirust agent be barium mahogany sulfonate, petroleum sodium sulfonate,
At least one of benzothiazole, BTA, decanedioic acid sodium, zinc naphthenate and alkenyl succinic acid.
10. a kind of preparation method of the excellent bentonite grease composition of antioxygenic property, methods described include：
(1) 1/2-2/3 lubricating base oil and antioxidant are added in fat kettle processed, are well mixed；
(2) bentonite thickening agent is added, is well mixed；
(3) dispersant is added, and is quickly stirred, until forming grease structure in kettle；
(4) 50-65 DEG C of holding 5-20min is warming up to, remaining base oil, other additives is added, is well mixed；
(5) ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, bentonite is thickened
The dosage of agent is 5-35 weight %, and the dosage of dispersant is 2-10 weight %, and the dosage of additive is 0.1-15 weight %, and it is special
Sign is that the antioxidant contains the compound of structure shown in formula (I)：
11. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
Dosage is 80-94 weight %, the dosage of bentonite thickening agent is 5-15 weight %, and the dosage of additive is 1-10 weight %.
12. the method according to claim 10 or 11, 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 %.
13. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
The dosage of compound be 0.2-1 weight %.
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| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| CN1946656A (en) * | 2004-02-17 | 2007-04-11 | 托马斯·E·约翰逊 | Methods, compositions, and apparatuses for forming macrocyclic compounds |
| CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
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|---|---|---|---|---|
| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| CN1946656A (en) * | 2004-02-17 | 2007-04-11 | 托马斯·E·约翰逊 | Methods, compositions, and apparatuses for forming macrocyclic compounds |
| CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
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