CN105586138B - Excellent compound lithium base grease of a kind of antioxygen property and preparation method thereof - Google Patents
Excellent compound lithium base grease of a kind of antioxygen property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the compound lithium base greases 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 lithium 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 compound lithium base grease of antioxygen property.The lithium base grease of the present invention has excellent oxidation resistance, while improves its viscosity, also has a degree of improvement to its anti-water drenching, and other performances are influenced less, still with good colloid stability etc..The addition of antioxidant is effectively improved the oxidation resistance of lubricating grease.The fat is enabled to be competent in the harsh working condition such as high temperature, high speed, high load capacity, more water.
Description
Technical field
The present invention relates to lubricating grease fields, and in particular, to a kind of excellent lithium of antioxygen property containing special additive
Base grease composition and preparation method thereof.
Background technology
Lithium base grease is that the 1940s is with fastest developing speed so far, and current output is maximum, application field it is most wide one
Kind multipurpose grease.National Lubricating Grease association is using a national lithium base grease proportion as its grease industry of measurement
The mark of technical merit.Lithium base grease has good colloid stability, mechanical stability, service life is long, range is wide etc.
Advantage is a kind of ideal multipurpose, long-life lubricating grease, but there is also some defects for lithium base grease：Such as inoxidizability
Energy is poor, abrasion resistance is poor, water repelling property is also poor.
The conventional production methods of lithium base grease are using 12- hydroxy stearic acids or stearic acid and hydroxide in base oil
Lithium reacts, and heating saponification obtains final product, such as US3980572.
In order to improve the performance of lithium base grease, formula and process aspect have all carried out different degrees of improvement.Such as
A kind of color is more shallow, the better lithium base of antioxygenic property lubricates by being prepared for the improvement of preparation process by CN101126045A
Fat；CN1718702A selects high viscosity mineral oil to be prepared for a kind of high extreme pressure lithium base lubricating grease；CN101880581A is improved instead
Temperature is answered, greatly improves product service life and water-resistance.US3681242、US3929651、US3711407、
CN1052890, CN1052891, CN1055384, CN101705141A report the composition and preparation method of lithium base grease, adopt
It is combined with 12- hydroxy lithium stearates and binary acid or boric acid, two component of salicylic lithium salts, also has and answered using three components
It closes；CN101921650 makes it be formed with soap molecule and acts synergistically, and then improve by adding in surfactant into formula
The arrangement mode of soap molecule and the ability of curing base oil are so as to improve the dropping point of lubricating grease；CN101993769A provides one
The preparation method of the lithium base grease of kind simple process, reduces production cost；CN101200670 provides a kind of comprehensive performance
The preparation method of preferable lithium base grease, especially to being damaged bearing with repair function；CN10148137 is using relatively low
The lithium base grease of high dropping point has been made in refining temperature, reduces the oil ageing in preparation process, improves lubricating grease
Oxidation stability.
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.
Invention content
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
Compound lithium base grease 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 lithium 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 lithium 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 lithium 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 0.2-2 weight %.
On the other hand, the present invention provides a kind of preparation method of the excellent compound lithium base grease of antioxygen property, institutes
The method of stating includes：
(1) by the lubricating base oil of 1/3-2/3, higher fatty acids and optional small molecule acid Hybrid Heating, it is warming up to 60-
90 DEG C, lithium source is added in, carries out saponification；
(2) 100-180 DEG C is warming up to, the lubricating base oil of 1/4-1/3 is added in, is refined；
(3) 190-220 DEG C is warming up to, is refined；
(4) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(5) it is ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of lithium base thickening agent prepared by aliphatic acid, optional small molecule acid and lithium source is 4-30 weight %, and the dosage of additive is
0.1-15 weight %, the additive contain the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-90 weight %, by height
The dosage of lithium base thickening agent prepared by grade aliphatic acid, optional small molecule acid and lithium source is 4-28 weight %, the dosage of additive
For 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 0.2-2 weight %.
The lithium base grease of the present invention has excellent oxidation resistance, while improves its viscosity, to its anti-water drenching
Also there is a degree of improvement, and other performances are influenced less, still with good colloid stability etc..Antioxidant adds
Enter to be effectively improved the oxidation resistance of lubricating grease.The fat is enabled to be competent in high temperature, high speed, high load capacity, more water etc. severe
Carve working condition.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing antioxidant.
Fig. 2 is the reaction equation of (b) the step of preparing antioxidant.
Fig. 3 is the reaction equation of (c) the step of preparing antioxidant.
Fig. 4 is the hydrogen spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 5 is the carbon spectrum spectrogram of antioxidant prepared by preparation example.
Fig. 6 is the mass spectrogram of antioxidant prepared by preparation example.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides the compound lithium base grease 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 lithium 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 lithium 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 0.2-2 weight %.
The present invention is directed to contain the compound of structure shown in formula (I) by the additive in compound lithium base grease and reality
Existing goal of the invention, even if compound lithium base grease has the excellent performances such as anti-oxidant.Therefore, for each in lithium 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 type of mineral oil, vegetable oil and synthetic oil, also there is no particular limitation, and it is normal that this field may be used
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, lithium base thickening agent can be lithium base thickening agent commonly used in the art, for example, can be that acid is anti-with lithium source
It should generate, acid includes 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, that is, lithium base thickening agent of the invention can be by
Higher fatty acids reacts generation with lithium source, generation can also be reacted with lithium source by higher fatty acids and small molecule acid.
Wherein, higher fatty acids can be the aliphatic acid of C12-C20, 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 can be the carboxylic acid of inorganic acid and/or C2-C11, preferably acetic acid, propionic acid, ethanedioic acid, oneself
At least one of diacid, azelaic acid, decanedioic acid, phosphoric acid, boric acid and terephthalic acid (TPA), more preferably decanedioic acid and/or nonyl two
Acid.
Wherein, lithium source is preferably lithium hydroxide.It will be understood by those skilled in the art that in actual use, generally
Add in lithium hydroxide aqueous solution, for lithium hydroxide aqueous solution concentration without particular/special requirement, such as can be 5-30 weight %.
Above-mentioned lithium base thickening agent may be used 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 containing in antirust agent, extreme pressure anti-wear additives and oiliness improver extremely
Few one kind.For antirust agent, extreme pressure anti-wear additives and oiliness improver type and content without particular/special requirement, this field routine may be used
Type and content.For example, antirust agent can be barium mahogany sulfonate and/or dinonyl naphthalene sulfonate barium, the content of antirust agent can be with
Account for the 0.01-4.5 weight % of lubricant composition total weight, preferably 0.1-2 weight %；Extreme pressure anti-wear additives can be amino sulphur
For ester and/or dialkyl dithiocarbamate, the content of extreme pressure anti-wear additives can account for lubricant composition total weight
0.5-12 weight %, preferably 0.5-5 weight %；Oiliness improver can be benzotriazole fatty amine, and the content of oiliness improver can be with
Account for the 0.2-8 weight % of lubricant composition total weight, preferably 0.5-3 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, 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 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 slufuric acid lithium 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, other than the bromination product shown in generation formula (III), the bromo production at also micro ortho position
Object generates, and is generated, but the amount of the bromination product at ortho position very pettiness without the bromination product of meta position, 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 be 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 slufuric acid lithium 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 third solvent,
In the presence of three catalyst, the bromination product that step (b) obtains is reacted with formula (IV) compound represented 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, third solvent is preferably selected from least one of dichloromethane, chloroform, toluene and tetrahydrofuran, more
Preferably dichloromethane.
In the present invention, third 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 bis- (diphenylphosphines
At least one of base) ferrocene (dppf)；Alkali is preferably selected from tert-butyl alcohol lithium, potassium tert-butoxide, cesium carbonate and lithium 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 range 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
Washing, drying, solvent is removed under reduced pressure in dilution, 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 lithium 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 third
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, the present invention is directed to contain structure shown in formula (I) by the additive in compound lithium base grease
Compound and realize goal of the invention, even if lubricant composition has the excellent performances such as anti-oxidant.Therefore, lithium base is lubricated
Without particular/special requirement method commonly used in the art may be used, for example, second aspect, the present invention also carries in the preparation method of fat
A kind of preparation method for the compound lithium base grease for having supplied antioxygen property excellent, this method include：
(1) by the lubricating base oil of 1/3-2/3, higher fatty acids and optional small molecule acid Hybrid Heating, it is warming up to 60-
90 DEG C, lithium source is added in, carries out saponification；
(2) 100-180 DEG C is warming up to, the lubricating base oil of 1/4-1/3 is added in, is refined；
(3) 190-220 DEG C is warming up to, is refined；
(4) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(5) it is ground 2-3 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of lithium base thickening agent prepared by aliphatic acid, optional small molecule acid and lithium source is 4-30 weight %, and the dosage of additive is
0.1-15 weight %, additive contain the compound of structure shown in formula (I)：
In the method for the present invention, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-
90 weight %, the dosage of lithium base thickening agent prepared by higher fatty acids, optional small molecule acid and lithium source are 4-28 weight %,
The dosage of additive is 1-10 weight %.
In the method for the present invention, the molar ratio of the total amount and lithium source of higher fatty acids and optional small molecule acid is preferably chemistry
Ratio is measured, lithium source can also excess 1-10 weight %.The molar ratio of higher fatty acids and optional small molecule acid is preferably 1:
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 lithium source preparation
The dosage of lithium base thickening agent counter can release the dosage of higher fatty acids, small molecule acid and lithium source, this is those skilled in the art
Known, details are not described herein.
In the present invention, can also not have as previously mentioned, " optional " refers to have." optional small molecule acid " refers to small
Molecule acid is a kind of optional component, can include the component, can not also include the component；" higher fatty acids with it is optional
The molar ratio of small molecule acid is 1:0.1-1 " is to refer to when containing small molecule acid, the molar ratio of higher fatty acids and small molecule acid
Preferably 1:0.1-1.In short, it will be understood by those skilled in the art that the lithium base thickening agent of the present invention can be by advanced fat
Fat acid reacts generation with lithium source, generation can also be reacted with lithium source by higher fatty acids and small molecule acid.
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)
It is selected as 0.1-3 weight %, more preferably 0.2-2 weight %.
In the method for the present invention, the lubricating base oil of 1/3-2/3, the lubricating base oil of 1/4-1/3 refer respectively to account for lubrication base
1/3-2/3,1/4-1/3 of plinth oil total amount.
In the method for the present invention step (1), the saponification time is preferably 1-4h.
In the method for the present invention step (2), the time of refining is preferably 0.2-1.5h, more preferably 0.5-1h.
In the method for the present invention step (3), the time of refining is preferably 5-15min.
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, lithium source, additive are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
The physico-chemical analysis method of product：Constituent content is measured by inductively coupled plasma ion emission spectroscopy method.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 200rpm), adds in 150ml
Methanol and 0.01mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyls of 0.1mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.3mol.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, the system after reaction is steamed solvent at 0.03MPa, 50 DEG C, then adds 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 slufuric acids lithium 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 tert-butyl alcohol lithium 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 slufuric acids lithium 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 compound lithium base grease of the present invention and preparation method thereof.
(1) by 344 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter) and 129.42 grams of 12- hydroxy stearic acids
In addition fat kettle, the agitating and heating under 180rpm is warming up to 80 DEG C, adds in 92.97 grams of lithium hydroxide aqueous solutions (a concentration of 8
Weight %), carry out saponification 3h；
(2) 150 DEG C are warming up to, adds in 344 grams of 150BS base oils, refines 30min；
(3) 200 DEG C are warming up to, refines 8min；
(4) 344 grams of 150BS base oils are added in, stirring is cooled to 100 DEG C, adds in 15 grams of S1,11 grams of barium mahogany sulfonates, and 10
Gram dithiodimethyl carbamic acid molybdenum, stirs evenly under 180rpm；
(5) 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：11 weight of 12- hydroxy lithium stearates
Measure %；86 weight % of lubricating base oil；S11.25 weight %；0.92 weight % of barium mahogany sulfonate；Dithiodimethyl amino first
Sour 0.83 weight % of molybdenum.
Embodiment 2
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 408 grams of 500SN base oils, (100 DEG C of viscosity are 11mm2/ s, similarly hereinafter) and 141.18 grams of 12- hydroxy stearic acids
In addition fat kettle, agitating and heating, is warming up to 70 DEG C at 200 rpm, and it is (a concentration of to add in 101.52 grams of lithium hydroxide aqueous solutions
15 weight %), carry out saponification 1h；
(2) 100 DEG C are warming up to, adds in 255 grams of 500SN base oils, refines 45min；
(3) 190 DEG C are warming up to, refines 10min；
(4) 357 grams of 500SN base oils are added in, stirring is cooled to 110 DEG C, adds in 10 grams of S1,13 grams of barium mahogany sulfonates, and 12
Gram dithiodimethyl carbamic acid molybdenum, stirs evenly at 200 rpm；
(5) 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：12 weight of 12- hydroxy lithium stearates
Measure %；85.09 weight % of lubricating base oil；S10.83 weight %；1.08 weight % of barium mahogany sulfonate；Dithiodimethyl amino
1 weight % of formic acid molybdenum.
Embodiment 3
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 530 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 79.42 grams of 12- hydroxy stearates
Acid is added in fat kettle processed, at 300 rpm agitating and heating, is warming up to 90 DEG C, and it is (a concentration of to add in 57.06 grams of lithium hydroxide aqueous solutions
11 weight %), carry out saponification 2h；
(2) 180 DEG C are warming up to, adds in 238 grams of PAO6 synthetic hydrocarbon oils, refines 55min；
(3) 220 DEG C are warming up to, refines 5min；
(4) 24 grams of PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 120 DEG C, adds in 5 grams of S1,10 grams of barium mahogany sulfonates, 10 grams
Dithiodimethyl carbamic acid molybdenum, stirs evenly at 300 rpm；
(5) 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：9 weight of 12- hydroxy lithium stearates
Measure %；88.7 weight % of lubricating base oil；S10.5 weight %；0.9 weight % of barium mahogany sulfonate；Dithiodimethyl amino first
Sour 0.9 weight % of molybdenum.
Embodiment 4
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 265 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) and 70.59 grams of 12- hydroxyls
Base stearic acid is added in fat kettle processed, the agitating and heating under 230rpm, is warming up to 60 DEG C, adds in 50.76 grams of lithium hydroxide aqueous solutions
(a concentration of 18 weight %) carries out saponification 4h；
(2) 130 DEG C are warming up to, adds in the miscella of 240 grams of 500SN and 150BS, refines 60min；
(3) 210 DEG C are warming up to, refines 6min；
(4) miscella of 296 grams of 500SN and 150BS is added in, stirring is cooled to 100 DEG C, adds in 12 grams of S1,7 grams of oil sulphurs
Sour barium, 8 grams of dithiodimethyl carbamic acid molybdenums, stir evenly under 230rpm；
(5) 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：8 weight of 12- hydroxy lithium stearates
Measure %；89 weight % of lubricating base oil；S11.33 weight %；0.78 weight % of barium mahogany sulfonate；Dithiodimethyl amino first
Sour 0.89 weight % of molybdenum.
Comparative example 1
Method according to embodiment 4 prepares lithium 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：8 weight of 12- hydroxy lithium stearates
Measure %；89 weight % of lubricating base oil；1.33 weight % of diphenylamines；0.78 weight % of barium mahogany sulfonate；Dithiodimethyl ammonia
0.89 weight % of base formic acid molybdenum.
Embodiment 5
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 458 grams of 500SN base oils, (100 DEG C of viscosity are 11mm2/ s, similarly hereinafter), 89.32 grams of 12- hydroxy stearic acids and
27.16 grams of azelaic acids are added in fat kettle processed, and the agitating and heating under 180rpm is warming up to 80 DEG C, adds in 224.62 grams of lithium hydroxides
Aqueous solution (a concentration of 16 weight %), carry out saponification 3h；
(2) 150 DEG C are warming up to, adds in 281 grams of 500SN base oils, refines 30min；
(3) 200 DEG C are warming up to, refines 8min；
(4) 281 grams of 500SN base oils are added in, stirring is cooled to 100 DEG C, add in 24.42 grams of S1,26.83 gram two thio two
Methyl carbamic acid molybdenum；2.8 grams of benzotriazole octadecylamines, stir evenly under 180rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：7.7 weight of 12- hydroxy lithium stearates
Measure %；2.4 weight % of azelaic acid lithium；85.4 weight % of lubricating base oil；S12 weight %；Dithiodimethyl carbamic acid molybdenum
2.3 weight %；0.2 weight % of benzotriazole octadecylamine.
Embodiment 6
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 430 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter), 135 grams of 12- hydroxy stearic acids and 40
Gram decanedioic acid is added in fat kettle processed, at 200 rpm agitating and heating, is warming up to 70 DEG C, adds in 320.5 grams of lithium hydroxide aqueous solutions
(a concentration of 20 weight %) carries out saponification 1h；
(2) 100 DEG C are warming up to, adds in 265 grams of 150BS base oils, refines 45min；
(3) 190 DEG C are warming up to, refines 10min；
(4) 265 grams of 150BS base oils are added in, stirring is cooled to 110 DEG C, adds in 4 grams of S1,12 grams of dithiodimethyl ammonia
Base formic acid molybdenum；10 grams of benzotriazole octadecylamines, stir evenly at 200 rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：12- hydroxy lithium stearates 12.1
Weight %；3.8 weight % of decanedioic acid lithium；80.9 weight % of lubricating base oil；S10.5 weight %；Dithiodimethyl amino first
Sour 1.4 weight % of molybdenum；1.3 weight % of benzotriazole octadecylamine.
Embodiment 7
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 351 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter), 54 grams of 12- hydroxy stearic acids and
16 grams of azelaic acids are added in fat kettle processed, at 300 rpm agitating and heating, are warming up to 90 DEG C, add in the water of 132.7 grams of lithium hydroxides
Solution (a concentration of 11 weight %) carries out saponification 2h；
(2) 180 DEG C are warming up to, adds in 216 grams of PAO6 synthetic hydrocarbon oils, refines 55min；
(3) 220 DEG C are warming up to, refines 2min；
(4) 216 grams of PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 120 DEG C, add in 7.36 grams of S1,17.91 gram two thio two
Methyl carbamic acid molybdenum；11.92 grams of benzotriazole octadecylamines, stir evenly at 300 rpm；
(5) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：6.2 weight of 12- hydroxy lithium stearates
Measure %；1.8 weight % of azelaic acid lithium；87.9 weight % of lubricating base oil；S10.8 weight %；Dithiodimethyl carbamic acid
2 weight % of molybdenum；1.3 weight % of benzotriazole octadecylamine.
Embodiment 8
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 335 grams of 500SN and 150BS, (100 DEG C of viscosity are 14mm2/ s, similarly hereinafter), 79.35 grams of 12- hydroxyls
Base stearic acid and 25.55 grams of decanedioic acid are added in fat kettle processed, and the agitating and heating under 230rpm is warming up to 60 DEG C, adds in 195.72
Gram lithium hydroxide aqueous solution (a concentration of 8 weight %) carries out saponification 4h；
(2) 130 DEG C are warming up to, adds in the miscella of 295 grams of 500SN and 150BS, refines 60min；
(3) 210 DEG C are warming up to, refines 6min；
(4) add in the miscella of 206 grams of 500SN and 150BS, stirring is cooled to 100 DEG C, add in 10 grams of S1,18.96 gram two
Thio dimethyl carbamic acid molybdenum；11 grams of benzotriazole octadecylamines, stir evenly under 230rpm；
(5) 3 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：9.1 weight of 12- hydroxy lithium stearates
Measure %；3.1 weight % of decanedioic acid lithium；83.6 weight % of lubricating base oil；S11 weight %；Dithiodimethyl carbamic acid molybdenum
2.1 weight %；1.1 weight % of benzotriazole octadecylamine.
Comparative example 2
Method according to embodiment 8 prepares lithium 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：9.1 weight of 12- hydroxy lithium stearates
Measure %；3.1 weight % of decanedioic acid lithium；83.6 weight % of lubricating base oil；1 weight % of diphenylamines；Dithiodimethyl amino first
Sour 2.1 weight % of molybdenum；1.1 weight % of benzotriazole octadecylamine.
Table 1
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Oxidation onset temperature：SH/
T0325；Stencil oil-dividing：SH/T 0324；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018.
Table 2
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Oxidation onset temperature：SH/
T0325；Stencil oil-dividing：SH/T 0324；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018.
It will be understood by those skilled in the art that dropping point is higher, the heat-resisting quantity of lubricating grease is better；Work cone penetration is got over
Small, the thickening performance of grease thickener is better；Oxidation onset temperature is higher, and the oxidation resistance of lubricating grease is better；Steel mesh point
Oil value is smaller, and the colloid stability of lubricating grease is better.
Embodiment 4 and comparative example 1 are compared, embodiment 8 and comparative example 2 are compared, it can be seen that the present invention
Lubricating grease have better inoxidizability, colloid stability.
The lithium base grease of the present invention has excellent oxidation resistance, while improves its viscosity, to its anti-water drenching
Also there is a degree of improvement, and other performances are influenced less, still with good colloid stability etc..Antioxidant adds
Enter to be effectively improved the oxidation resistance of lubricating grease.The fat is enabled to be competent in high temperature, high speed, high load capacity, more water etc. severe
Carve working condition.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that 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 (20)
1. a kind of excellent composite barium-base grease composition of antioxygen property, described on the basis of the weight of lubricant composition
Lubricant composition includes following components：The lubricating base oil of 65-95 weight %, the composite barium-base thickening agent of 4-30 weight % and
The additive of 0.1-15 weight %, which is characterized in that the additive contains the compound of structure shown in formula (I)：
2. lubricant composition according to claim 1, wherein, on the basis of the weight of lubricant composition, the profit
Grease composition includes following components：The lubricating base oil of 75-88 weight %, the composite barium-base thickening agent of 4-28 weight % and
The additive of 0.1-5 weight %.
3. lubricant composition according to claim 1 or 2, wherein, on the basis of the weight of lubricant composition, formula
(I) content of the compound of structure shown in is 0.1-3 weight %.
4. lubricant composition according to claim 3, wherein, on the basis of the weight of lubricant composition, formula (I) institute
The content for showing the compound of structure is 0.2-1 weight %.
5. lubricant composition according to claim 1 or 2, wherein, the lubricating base oil is mineral oil, vegetable oil and
At least one of synthetic oil.
6. lubricant composition according to claim 1 or 2, wherein, the composite barium-base thickening agent is anti-with barium source for acid
It should generate, the acid includes higher fatty acids and small molecule acid.
7. lubricant composition according to claim 6, wherein, aliphatic acid of the higher fatty acids for 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
Acid and at least one of 12- hydroxy stearic acids, the small molecule acid be in terephthalic acid (TPA), azelaic acid and decanedioic acid at least
It is a kind of.
9. lubricant composition according to claim 8, wherein, the higher fatty acids is stearic acid and/or 12- hydroxyls
Stearic acid.
10. lubricant composition according to claim 6, wherein, the barium source is barium hydroxide.
11. lubricant composition according to claim 1 or 2, wherein, the additive also contains antirust agent.
12. lubricant composition according to claim 11, wherein, the antirust agent is barium mahogany sulfonate, dinonyl benzene
At least one of barium sulfonate and Lanolin Calcium Soap.
13. a kind of preparation method of the excellent composite barium-base grease composition of antioxygen property, the method includes：
(1) by partial lubrication base oil and higher fatty acids, small molecule acid Hybrid Heating, 90-110 DEG C is warming up to, adds in barium source,
Carry out saponification；
(2) 170-220 DEG C is warming up to be refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) it is ground 2-4 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by higher aliphatic
The dosage of composite barium-base thickening agent prepared by acid, small molecule acid and barium source is 4-30 weight %, and the dosage of additive is 0.1-15
Weight %, which is characterized in that the additive contains the compound of structure shown in formula (I)：
14. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
Dosage is 75-88 weight %, the dosage of composite barium-base thickening agent prepared by higher fatty acids, small molecule acid and barium source is 4-28
Weight %, the dosage of additive is 0.1-5 weight %.
15. the method according to claim 13 or 14, wherein, on the basis of the weight of lubricant composition, shown in formula (I)
The dosage of the compound of structure is 0.1-3 weight %.
16. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
Compound dosage be 0.2-1 weight %.
17. the method according to claim 13 or 14, wherein, the partial lubrication base oil and the remaining lubrication base
The weight ratio of oil is 50-75:25-50.
18. the method according to claim 13 or 14, wherein, the total amount and barium source of higher fatty acids and small molecule acid are rubbed
You are than being stoichiometric ratio；The molar ratio of higher fatty acids and small molecule acid is 1:0.1-1.
19. the method according to claim 13 or 14, wherein, in step (1), the time of saponification is 1-3h.
20. the method according to claim 13 or 14, wherein, in step (2), the time of the refining is 5-20min.
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|---|---|---|---|---|
| US5407592A (en) * | 1991-07-23 | 1995-04-18 | Mobil Oil Corporation | Multifunctional additives |
| US5560854A (en) * | 1992-09-18 | 1996-10-01 | Nissan Motor Co., Ltd. | Working fluid composition for HFC refrigerant compressor containing benzotriazole derivatives, and a process for improving lubrication in a compressor |
| US5846917A (en) * | 1995-04-04 | 1998-12-08 | Mobil Oil Corporation | Phenolic imidazoline antioxidants |
| CN102433203A (en) * | 2011-10-24 | 2012-05-02 | 中国石油化工股份有限公司 | Lithium-based lubricating grease composition and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080090743A1 (en) * | 2006-10-17 | 2008-04-17 | Mathur Naresh C | Compounds and methods of making the compounds |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407592A (en) * | 1991-07-23 | 1995-04-18 | Mobil Oil Corporation | Multifunctional additives |
| US5560854A (en) * | 1992-09-18 | 1996-10-01 | Nissan Motor Co., Ltd. | Working fluid composition for HFC refrigerant compressor containing benzotriazole derivatives, and a process for improving lubrication in a compressor |
| US5846917A (en) * | 1995-04-04 | 1998-12-08 | Mobil Oil Corporation | Phenolic imidazoline antioxidants |
| CN102433203A (en) * | 2011-10-24 | 2012-05-02 | 中国石油化工股份有限公司 | Lithium-based lubricating grease composition and preparation method |
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