CN105567403B - Excellent complex lithium-calcium base grease composition of Wear vesistance and preparation method thereof - Google Patents
Excellent complex lithium-calcium base grease composition of Wear vesistance and preparation method thereof Download PDFInfo
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- CN105567403B CN105567403B CN201410571583.3A CN201410571583A CN105567403B CN 105567403 B CN105567403 B CN 105567403B CN 201410571583 A CN201410571583 A CN 201410571583A CN 105567403 B CN105567403 B CN 105567403B
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- MHLMJBQJKZOTNJ-UHFFFAOYSA-N Sc1nnc(Sc(cc2)ccc2Ns2nc3ccccc3[s]2)[s]1 Chemical compound Sc1nnc(Sc(cc2)ccc2Ns2nc3ccccc3[s]2)[s]1 MHLMJBQJKZOTNJ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses the complex lithium-calcium base grease compositions that a kind of Wear vesistance 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 complex lithium-calcium base thickening agent of 5 35 weight % and 0.1 15 weight %, the additive contain the compound of structure shown in formula (I).The present invention also provides the preparation methods of the excellent complex lithium-calcium base grease composition of Wear vesistance.The complex lithium-calcium base grease composition of the present invention, due to containing multipurpose additive, drastically increase the anti-attrition ability and oxidation resistance of lubricating grease, the other performance of complex lithium-calcium base grease is influenced simultaneously little, still there is splendid heat-resisting quantity, colloid stability, water proofing property etc. so that the lubricant composition can 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 Wear vesistance containing special additive is excellent to answer
Close lithium-calcium base grease composition and preparation method thereof.
Background technology
Different metals assigns lubricating grease different property.Recently as the development of modern industry, bearing, automobile, print
The industrial departments such as dye, mine, metallurgy, aerospace to the inoxidizability of lubricating grease, high and low temperature performance and extreme pressure anti-wear, water-resistance,
Mechanical stability etc. proposes increasingly harsher requirement, and complex thickener class lubricating grease has obtained very big development.Have a large amount of
Patent inquires into the performance of complex lithium-calcium base grease.
CN85108442A reports " binary metallic based grease composition and preparation method thereof ", is prepared using two step method
Complex lithium-calcium base grease, said composition have good heat-resisting quantity, extreme pressure property and anti-corrosive properties, but this preparation method technique
It is complicated, it is not easy to control and the water resistant shear stability of product, cryogenic property are not described；CN86103103A discloses a step
Method prepares the preparation process of lithium-calcium base grease, and product obtained has excellent shear stability and good water-resistance and excellent
Different colloid stability, but dropping point is relatively low (180 DEG C)；US5350531 reports a kind of complex lithium-calcium base grease
Preparation method, lubricating grease made from this method have good mechanical stability, and it is 25 that 100,000 times, which are cut difference, but its dropping point
Less than 200 DEG C；CN1252434A reports a kind of lithium calcium base constituent and its preparation process, and product is sheared with good water resistant
Stability, mechanical stability, resistant of high or low temperature, extreme pressure anti-wear and protective；CN101921649A into system by adding in
Surfactant is prepared for a kind of complex lithium-calcium base grease of high dropping point；CN101792689A is replaced with lithium hydroxide suspension
Monohydrate lithium hydroxide provides a kind of simple preparation method of high-performance complex lithium-calcium base grease.
Recently as the development of modern industry, the industrial departments such as bearing, automobile, printing and dyeing, mine, metallurgy, aerospace are to profit
The quality of consistent lubricant proposes increasingly harsher requirement, and many lubricant housings are all disposably to fill fat, in the process of running no longer
Supplement is replaced, so higher to the abrasion resistance requirement of fat.
The content of the invention
The purpose of the invention is to meet the high request to the abrasion resistance of lubricating grease, it is excellent to provide a kind of Wear vesistance
Complex lithium-calcium base grease composition and preparation method thereof.
The present inventor has found that the additive in lubricant composition contains structure shown in formula (I) under study for action
Multipurpose additive：
It can make lubricant composition that there are the performances such as excellent anti-attrition is anti-oxidant.
Therefore, to achieve these goals, on the one hand, the present invention provides the complex lithium-calcium bases that a kind of Wear vesistance is excellent
Lubricant composition, on the basis of the weight of lubricant composition, the lubricant composition includes following components：65-95 weights
Measure lubricating base oil, the complex lithium-calcium base thickening agent of 5-35 weight % and the additive of 0.1-15 weight % of %, the addition
Agent contains the compound of structure shown in formula (I)：
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 complex lithium-calcium base thickening agent of 8-30 weight % and 0.5-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the content of the compound of structure shown in formula (I) is 0.1-10
Weight %, more preferably 1-5 weight %.
On the other hand, the present invention provides a kind of preparation sides of the excellent complex lithium-calcium base grease composition of Wear vesistance
Method, the described method includes：
(1) by partial lubrication base oil and higher fatty acids Hybrid Heating, calcium source is added in, carries out the first saponification, so
Small molecule acid and lithium source are added in backward system, carries out the second saponification；
(2) and then at 180-230 DEG C refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of complex lithium-calcium base thickening agent prepared by aliphatic acid, small molecule acid, lithium source and calcium source is 5-35 weight %, the use of additive
It measures as 0.1-15 weight %, the additive contains the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-90 weight %, by height
The dosage of complex lithium-calcium base thickening agent prepared by grade aliphatic acid, small molecule acid, lithium source and calcium source is 8-30 weight %, additive
Dosage is 0.5-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the dosage of the compound of structure shown in formula (I) is 0.1-10
Weight %, more preferably 1-5 weight %.
The complex lithium-calcium base grease composition of the present invention, due to containing multipurpose additive, drastically increases lubricating grease
Anti-attrition ability and oxidation resistance, while the other performance of complex lithium-calcium base grease is influenced it is little, still with splendid
Heat-resisting quantity, colloid stability, water proofing property etc. so that the lubricant composition can be competent in high temperature, high speed, high load capacity, more
The harshness working condition such as water.
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 multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 4 is the carbon spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 5 is the mass spectrogram of multipurpose additive prepared by preparation example.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides the complex lithium-calcium base grease composition that a kind of Wear vesistance is excellent, with lubricant composition
On the basis of weight, lubricant composition includes following components：The lubricating base oil of 65-95 weight %, 5-35 weight % it is compound
The additive of lithium calcium base thickening agent and 0.1-15 weight %, additive contain the compound of structure shown in formula (I)：
In the present invention, what multipurpose additive 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 addition of the lubricating base oil of 70-90 weight %, the complex lithium-calcium base thickening agent of 8-30 weight % and 0.5-10 weight %
Agent.
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)
0.1-10 weight %, more preferably 1-5 weight %.
It is contemplated that contain the chemical combination of structure shown in formula (I) by the additive in complex lithium-calcium base grease composition
Object and realize goal of the invention, even if complex lithium-calcium base grease composition has the performances such as excellent anti-attrition is anti-oxidant.Therefore, it is right
The selection of each conventional constituents, does not limit specifically in complex lithium-calcium base grease.
In the present invention, lubricating base oil can be lubricating base oil commonly used in the art, such as can be mineral oil,
At least one of vegetable oil and synthetic oil.100 DEG C of kinematic viscosity of lubricating base oil are preferably 4-60mm2/ s, more preferably 5-
32mm2/s.For the specific species of mineral oil, vegetable oil and synthetic oil, also there is no particular limitation, and it is normal that this field may be employed
Mineral oil, vegetable oil and synthetic oil, for example, mineral oil can select paraffinic base, cycloalkyl series, vegetable oil can be castor
At least one of sesame oil, rapeseed oil, peanut oil and soybean oil etc., synthetic oil can be poly-a-olefin oil (PAO), Esters oil, fluorine
At least one of oil and silicone oil etc..
In the present invention, complex lithium-calcium base thickening agent can be complex lithium-calcium base thickening agent commonly used in the art, for example, can be with
It is generated for acid and lithium source and calcium source reaction, acid includes higher fatty acids and small molecule acid.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, be preferably lauric acid, palmitic acid, stearic acid and 12-
At least one of hydroxy stearic acid, more preferably stearic acid and/or 12- hydroxy stearic acids.
Wherein, small molecule acid is preferably the dicarboxylic acids of C6-C10, more preferably terephthalic acid (TPA), azelaic acid and decanedioic acid
At least one of.
Wherein, lithium source is preferably lithium hydroxide, and calcium source is preferably calcium hydroxide.
Above-mentioned complex lithium-calcium base thickening agent may be employed the thinkable various methods of those skilled in the art institute and obtain.
In the present invention, since the multipurpose additive of structure shown in formula (I) and other additives have preferable compatibility, because
This, according to the use needs of lubricating grease, additive of the invention can also contain other antioxidant, extreme pressure anti-wear additives and antirust
At least one of agent.
In the present invention, for other antioxidant, extreme pressure anti-wear additives, antirust agent species and content without particular/special requirement, can
With using the species and content of this field routine.For example, antioxidant can be arylamine kind antioxidant, be preferably diphenylamines, phenyl-
At least one of alpha-naphthylamine and di-iso-octyldiphenylamine, more preferably di-iso-octyldiphenylamine, the content of antioxidant can account for
The 0.01-5 weight % of lubricant composition total weight, preferably 0.1-2.5 weight %；Extreme pressure anti-wear additives can be two thio dioxanes
Base trbasic zinc phosphate, two thio dialkyl amido formic acid molybdenums, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), two
At least one of butyl antimony dithiocarbamate, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide, pole
The content of pressure antiwear additive can account for the 0.5-12 weight % of lubricant composition total weight, be preferably 0.5-5 weight %；Antirust agent
Can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid at least
One kind, the content of antirust agent can account for the 0.01-4.5 weight % of lubricant composition total weight, be preferably 0.1-2 weight %.
In the present invention, the preparation method of the compound of structure preferably includes shown in formula (I)：
(a) aniline, sulfur chloride and 4- chloroanilines are reacted, generate the intermediate M shown in formula (II),
(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains is carried out nucleophilic in alkaline conditions to take
Generation reaction, generates the multipurpose additive shown in formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroanilines react is preferably included：
(i) under an inert atmosphere, in the first solvent, aniline is fully reacted with sulfur chloride at -20-0 DEG C；
(ii) 4- chloroanilines are added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.
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.
In step (i) of the present invention, the first solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene and dioxy six
At least one of ring, more preferably dichloromethane and/or tetrahydrofuran, are still more preferably dichloromethane.
In the present invention in step (i), fully reacted and refer to that the reaction was complete, i.e., reaction raw materials are reacted completely.
Method commonly used in the art may be employed to be monitored reaction, to confirm that the reaction was complete, such as thin layer chromatography may be employed
(TLC) or the methods of gas-chromatography, is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) fully reaction, by reactant
The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroanilines and carries out reaction 1-3h.It, can be further under the preferable case
Improve reaction yield.
In step (ii) of the present invention, the feed postition of 4- chloroanilines is preferably to add in by several times, such as can divide 3-4 times and add
Enter.Under the preferable case, reaction yield can be further improved.When being added in for gradation, each addition can be identical,
Can not also be same, in order to easy to operate, preferably each addition is identical.
In step (ii) of the present invention, react 1-3h, stop reaction mode can be those skilled in the art it is contemplated that
Various modes, be quenched for example, quencher can be added in, quencher can be quencher commonly used in the art, such as can
Think saturated salt solution.
In the present invention, the dosage of aniline, sulfur chloride and 4- chloroanilines is substantially equimolar amounts, but aniline and sulfur chloride can
With appropriate excessive.The molar ratio of aniline, sulfur chloride and 4- chloroanilines is preferably 0.9-1.5：0.9-1.5：0.8-1.2.
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 washing, drying, solvent is removed under reduced pressure, for example,
By the reaction system after being quenched respectively with distilled water and saturated common salt water washing, then anhydrous calcium chloride is added at 15-30 DEG C
Or the drier such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove drier, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroanilines are reacted is as shown in Figure 1, figure
In 1, the first solvent is not construed as limiting the scope of the present invention using dichloromethane, purpose by way of example only.
In step (b) of the present invention, the condition of nucleophilic substitution preferably includes：Under an inert atmosphere, in the second solvent,
Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, then add in intermediate
M is fully reacted.I.e. alkaline condition is provided by alkaline reagent.
" inert atmosphere ", " fully being reacted " are as previously mentioned, details are not described herein.
In the present invention, intermediate M is preferably slowly added to, such as can be added in by several times, can generally divide 3-4 addition.
Under the preferable case, reaction yield can be further improved.When being added in for gradation, each addition can be identical, also may be used
With difference, in order to easy to operate, preferably each addition is identical.
In the present invention, the second solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyls
At least one of amine, more preferably dichloromethane and/or n,N-Dimethylformamide, are still more preferably N, N- dimethyl
Formamide.
In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc.
Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalescence examination
The molar ratio of agent and intermediate M are preferably 0.9-3.0：0.9-5.0：0.8-1.5.
In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole
On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.
In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Shown, in Fig. 2, alkaline reagent does not form the scope of the present invention and limits using potassium carbonate, purpose by way of example only
System.
It will be understood by those skilled in the art that purer final product, i.e. multiple-effect of the invention add in order to obtain
Add agent, the method for the invention for preparing multipurpose additive, which preferably further includes, post-processes the system after reaction, the side of post processing
Formula can include washing, drying, solvent is removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume
In ethyl ester (or dichloromethane), respectively with distilled water and saturated common salt water washing, then anhydrous calcium chloride is added at 15-30 DEG C
Or the drier such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove drier, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain final product.
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.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine
Dosage, this is known to those skilled in the art, and details are not described herein.
As described above, it is contemplated that contained by the additive in complex lithium-calcium base grease composition shown in formula (I)
The compound of structure and realize goal of the invention, even if lubricant composition has the performances such as excellent anti-attrition is anti-oxidant.Therefore, it is right
In complex lithium-calcium base grease preparation method without particular/special requirement, method commonly used in the art may be employed, for example, second
Aspect, the present invention also provides a kind of preparation method of the excellent complex lithium-calcium base grease composition of Wear vesistance, this method
Including：
(1) by partial lubrication base oil and higher fatty acids Hybrid Heating, calcium source is added in, carries out the first saponification, so
Small molecule acid and lithium source are added in backward system, carries out the second saponification；
(2) and then at 180-230 DEG C refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of complex lithium-calcium base thickening agent prepared by aliphatic acid, small molecule acid, lithium source and calcium source is 5-35 weight %, the use of additive
It measures as 0.1-15 weight %, additive contains the compound of structure shown in formula (I)：
In the method for the present invention, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-
90 weight %, the dosage of the complex lithium-calcium base thickening agent prepared by higher fatty acids, small molecule acid, lithium source and calcium source are 8-30 weights
% is measured, the dosage of additive is 0.5-10 weight %.
In the method for the present invention, the first saponification is that higher fatty acids is reacted with calcium source, and higher fatty acids is compared with calcium source
It is excessive, then add in small molecule acid and lithium source, the second saponification be lithium source respectively with the sour and remaining higher aliphatic of small molecule
Acid reaction, the molar ratio of lithium source and the total amount of the sour and remaining higher fatty acids of small molecule is stoichiometric ratio, and lithium source can also
Excessive 1-10 weight %.Therefore, in the method for the present invention, obtained complex lithium-calcium base thickening agent is higher fatty acid calcium, advanced fat
Fat acid lithium and small molecule acid lithium.
In the method for the present invention, the molar ratio of higher fatty acids and small molecule acid is preferably 1:0.1-1.Calcium source is preferably hydrogen-oxygen
Change calcium, lithium source is preferably lithium hydroxide, and the molar ratio of calcium hydroxide and lithium hydroxide is preferably 1:1-50, more preferably 1:5-
20.It is it will be understood by those skilled in the art that compound according to being prepared by higher fatty acids, small molecule acid, lithium source and calcium source
The dosage of lithium calcium base thickening agent counter can release the dosage of higher fatty acids, small molecule acid, lithium source and calcium source, this is this field
Well known to technical staff, details are not described herein.
In the method for the present invention, on the basis of the weight of lubricant composition, the dosage of the compound of structure is excellent shown in formula (I)
Elect 0.1-10 weight % as, more preferably 1-5 weight %.
It will be understood by those skilled in the art that in the method for the present invention, the dosage of lubricating base oil is partial lubrication base
The sum of the dosage of plinth oil and the dosage of remaining lubricating base oil.Partial lubrication base oil and the weight ratio of remaining lubricating base oil are excellent
Elect 50-80 as:20-50.
In the method for the present invention step (1), the temperature of the first saponification is preferably 80-105 DEG C, and the time is preferably 10-
30min；The temperature of second saponification is preferably 80-120 DEG C, and the time is preferably 10-30min.
As described above, the second saponification is lithium source higher fatty acids reaction sour and remaining with small molecule respectively, therefore,
In step (1), after the first saponification has been carried out, small molecule acid is preferably first added in, continues to stir, then adds in lithium source, make
Lithium source and small molecule are sour and remaining higher fatty acids carries out the second saponification.
In the method for the present invention step (2), preferably to be refined at 190-210 DEG C, the refining time is preferably 1-25min,
More preferably 5-20min.
Each step of the method for the present invention preferably carries out under stiring, can be this field for mixing speed without particular/special requirement
Conventional mixing speed, for example, mixing speed can be 20-500rpm.
Lubricating base oil, higher fatty acids, small molecule acid, additive are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
The monitoring method that the reaction was complete：Thin-layer chromatography chromatography (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
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 spectrum), high resolution mass spectrum.
Preparation example
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 300rpm), adds in 150ml
Dichloromethane, then add in 0.2mol sulfur chloride, after being fully cooled in ice-water bath, add in the aniline of 0.2mol.Monitoring
Ice-water bath is removed to after the reaction was complete, 25 DEG C is placed at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine
Aniline is reacted, and each addition is identical, adds in 4- chloroanilines 0.15mol altogether.30ml saturations are added in after when sustained response 2 is small
Reaction is quenched in saline solution, and then reaction system is transferred in separatory funnel, respectively with 50ml distilled water and 50ml saturated salt solutions
Washing, and add in 10g anhydrous sodium sulfates dry 20min at 25 DEG C.Filtrate after filtering is evaporated off molten under 40 DEG C, 0.05MPa
Agent obtains intermediate M1.
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 400rpm), adds in 150ml
DMF (n,N-Dimethylformamide), then add in 0.2mol dimercapto-1,3,4-thiadiazoles and 0.2mol potassium carbonate,
The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each addition is identical, adds in altogether
Intermediate M10.12mol.Then reaction system is added in 250ml ethyl acetate, and is transferred to separatory funnel by monitoring to the reaction was complete
In, respectively with 100ml distilled water (twice) and 50ml saturated common salt water washings, and add in 15g anhydrous sodium sulfates and done at 25 DEG C
Dry 20min.Solvent is evaporated off under 40 DEG C, 0.03MPa in filtrate after filtering, obtains final product S1.It is 76% to calculate gross production rate.
The physico-chemical analysis data of product are as follows：Sulfur content, 41.3%；Nitrogen content, 13.9%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and
Fig. 5.
Physico-chemical analysis data, Fig. 3, Fig. 4 and Fig. 5 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 complex lithium-calcium base grease composition of the present invention and preparation method thereof.
(1) by 573 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and 48.89 grams of 12- hydroxy stearic acids
In addition fat kettle, 80 DEG C are heated under 400rpm stirrings, the suspension containing 54.13 grams of calcium hydroxide is added in and carries out soap
Change reaction 10min, then add in 16.45 grams of decanedioic acid and the aqueous solution containing 11.73 gram of one hydronium(ion) lithia, carry out saponification
React 30min；
(2) 190 DEG C are warming up to, refines 5min；
(3) 192 grams of 500SN base oils are added in, treats that temperature is cooled to 100 DEG C, adds in 17 grams of S1, are stirred under 400rpm equal
It is even；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：2.1 weight of 12- hydroxy stearic acid calciums
Measure %；3.9 weight % of 12- hydroxy lithium stearates；2 weight % of decanedioic acid lithium；90 weight % of lubricating base oil；S12 weight %.Hydrogen
The molar ratio of calcium oxide and lithium hydroxide is 1:5.
Embodiment 2
The present embodiment is used to illustrate complex lithium-calcium base grease composition of the present invention and preparation method thereof.
(1) by 182 grams of 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter) and 98.35 grams of 12- hydroxy stearic acids
In addition fat kettle, 105 DEG C are heated under 80rpm stirrings, the suspension containing 3.12 grams of calcium hydroxide is added in and carries out soap
Change reaction 20min, then add in 46.21 grams of azelaic acids and the aqueous solution containing 33.63 gram of one hydronium(ion) lithia carries out saponification
React 20min；
(2) 210 DEG C are warming up to, refines 8min；
(3) 180 grams of 150BS base oils are added in, treats that temperature is cooled to 120 DEG C, adds in 5.2 grams of S1, are stirred under 80rpm equal
It is even；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：12- hydroxy stearic acid calciums 2.52
Weight %；16.98 weight % of 12- hydroxy lithium stearates；9.5 weight % of azelaic acid lithium；70 weight % of lubricating base oil；S11 weights
Measure %.The molar ratio of calcium hydroxide and lithium hydroxide is 1:19.
Embodiment 3
The present embodiment is used to illustrate complex lithium-calcium base grease composition of the present invention and preparation method thereof.
(1) by 200 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) add in and make with 60.6 grams of stearic acid
In fat kettle, 100 DEG C are heated under 300rpm stirrings, the suspension containing 3.25 grams of calcium hydroxide is added in and carries out saponification
Then 30min adds in 14.16 grams of terephthalic acid (TPA)s and the aqueous solution containing 16.59 gram of one hydronium(ion) lithia, it is anti-to carry out saponification
Answer 15min；
(2) 195 DEG C are warming up to, refines 15min；
(3) 137.5 grams of PAO6 synthetic hydrocarbon oils are added in, treats that temperature is cooled to 105 DEG C, adds in 22.5 grams of S1, at 300 rpm
It stirs evenly；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：2.87 weight % of calcium stearate；
13.75 weight % of lithium stearate；3.38 weight % of terephthalic acid (TPA) lithium；75 weight % of lubricating base oil；S15 weight %.Hydrogen-oxygen
The molar ratio for changing calcium and lithium hydroxide is 1:9.
Embodiment 4
The present embodiment is used to illustrate complex lithium-calcium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 674.5 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2It is/s, similarly hereinafter) hard with 103.7 grams
Resin acid is added in fat kettle processed, and 90 DEG C are heated under 500rpm stirrings, add in the suspension containing 3.25 grams of calcium hydroxide into
Then row saponification 15min adds in 38.24 grams of decanedioic acid and the aqueous solution containing 30.89 gram of one hydronium(ion) lithia, carry out
Saponification 10min；
(2) 200 DEG C are warming up to, refines 10min；
(3) miscella of 200 grams of 500SN and 150BS is added in, treats that temperature is cooled to 120 DEG C, adds in 32 grams of S1,
It is stirred evenly under 500rpm；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：1.69 weight % of calcium stearate；
9.72 weight % of lithium stearate；3.59 weight % of decanedioic acid lithium；82 weight % of lubricating base oil；S13 weight %.Calcium hydroxide with
The molar ratio of lithium hydroxide is 1:12.
Comparative example 1
Method according to embodiment 4 prepares complex lithium-calcium base grease, unlike, it is added without S1.Properties of product such as table 1
It is shown.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：1.74 weight % of calcium stearate；
10.02 weight % of lithium stearate；3.7 weight % of decanedioic acid lithium；84.54 weight % of lubricating base oil.
Table 1
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Aoxidize initial temperature：PDSC；
Stencil oil-dividing：SH/T0324；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018；Water drenches number of dropouts：SH/T 0109；
Coefficient of friction：SH/T 0847.
It will be understood by those skilled in the art that dropping point is higher, the high temperature resistance of lubricating grease is better；Work cone penetration
Smaller, the thickening performance of grease thickener is better；Oxidation initial temperature is higher, and the antioxygenic property of lubricating grease is better；Steel mesh
Oil is divided to be worth smaller, the colloid stability of lubricating grease is better；Water leaching number of dropouts is smaller, and the water resistance of lubricating grease is better；Friction system
Number is smaller, and the antifriction performance of lubricating grease is better.
By embodiment 4 compared with comparative example 1 as can be seen that the present invention lubricating grease have better heat-resisting quantity,
Inoxidizability, colloid stability, water proofing property and antifriction performance.
The complex lithium-calcium base grease composition of the present invention, due to containing multipurpose additive, drastically increases lubricating grease
Anti-attrition ability and oxidation resistance, while the other performance of complex lithium-calcium base grease is influenced it is little, still with splendid
Heat-resisting quantity, colloid stability, water proofing property etc. so that the lubricant composition can be competent in high temperature, high speed, high load capacity, more
The harshness working condition such as water.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (25)
1. a kind of excellent complex lithium-calcium base grease composition of Wear vesistance, on the basis of the weight of lubricant composition, institute
Stating lubricant composition includes following components：The complex lithium-calcium base thickening of the lubricating base oil, 5-35 weight % of 65-95 weight %
Agent 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 70-90 weight %, the complex lithium-calcium base thickening agent of 8-30 weight % and
The additive of 0.5-10 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 0.1-10 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 1-5 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 complex lithium-calcium base thickening agent is acid and lithium source
It reacts and generates with calcium source, the acid includes higher fatty acids and small molecule acid.
7. lubricant composition according to claim 6, wherein, the higher fatty acids is the aliphatic acid of C12-C25, institute
State the dicarboxylic acids that small molecule acid is C6-C10.
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 in terephthalic acid (TPA), azelaic acid and decanedioic acid at least
It is a kind of.
9. lubricant composition according to claim 6, wherein, the lithium source is lithium hydroxide, and the calcium source is hydrogen-oxygen
Change calcium.
10. lubricant composition according to claim 1 or 2, wherein, the additive also containing other antioxidant,
At least one of extreme pressure anti-wear additives and antirust agent.
11. lubricant composition according to claim 10, wherein, the antioxidant is arylamine kind antioxidant.
12. lubricant composition according to claim 11, wherein, the antioxidant is diphenylamines, phenyl-α-naphthylamine and
At least one of di-iso-octyldiphenylamine.
13. lubricant composition according to claim 10, 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.
14. lubricant composition according to claim 10, wherein, the antirust agent is barium mahogany sulfonate, mahogany acid
At least one of sodium, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
15. the preparation method of lubricant composition described in claim 1, the described method includes：
(1) by partial lubrication base oil and higher fatty acids Hybrid Heating, calcium source is added in, carries out the first saponification, Ran Houxiang
Small molecule acid and lithium source are added in system, carries out the second saponification；
(2) and then at 180-230 DEG C refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-3 times by three-roller.
16. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
The use for the complex lithium-calcium base thickening agent that dosage is prepared for 70-90 weight %, by higher fatty acids, small molecule acid, lithium source and calcium source
It measures as 8-30 weight %, the dosage of additive is 0.5-10 weight %.
17. the method according to claim 15 or 16, wherein, on the basis of the weight of lubricant composition, shown in formula (I)
The dosage of the compound of structure is 0.1-10 weight %.
18. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
Compound dosage be 1-5 weight %.
19. the method according to claim 15 or 16, wherein, the partial lubrication base oil and the remaining lubrication base
The weight ratio of oil is 50-80:20-50.
20. the method according to claim 15 or 16, wherein, the molar ratio of higher fatty acids and small molecule acid is 1:0.1-
1。
21. the method according to claim 15 or 16, wherein, the calcium source is calcium hydroxide, and the lithium source is hydroxide
The molar ratio of lithium, calcium hydroxide and lithium hydroxide is 1:1-50.
22. according to the method for claim 21, wherein, the molar ratio of calcium hydroxide and lithium hydroxide is 1:5-20.
23. the method according to claim 15 or 16, wherein, in step (1), the temperature of the first saponification is 80-105
DEG C, time 10-30min；The temperature of second saponification is 80-120 DEG C, time 10-30min.
24. the method according to claim 15 or 16, wherein, it in step (2), is refined, is refined at 190-210 DEG C
Time is 1-25min.
25. according to the method for claim 24, wherein, in step (2), being refined at 190-210 DEG C, the time is refined
For 5-20min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| JPH05142725A (en) * | 1991-11-22 | 1993-06-11 | Fuji Photo Film Co Ltd | Color reversal photographic sensitive material |
| 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 |
| CN102977979A (en) * | 2012-12-17 | 2013-03-20 | 江苏龙蟠石化有限公司 | Composite lithium-calcium base lubricating grease and preparation method thereof |
-
2014
- 2014-10-23 CN CN201410571583.3A patent/CN105567403B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| JPH05142725A (en) * | 1991-11-22 | 1993-06-11 | Fuji Photo Film Co Ltd | Color reversal photographic sensitive material |
| CN1946656A (en) * | 2004-02-17 | 2007-04-11 | 托马斯·E·约翰逊 | Methods, compositions, and apparatuses for forming macrocyclic compounds |
| CN102977979A (en) * | 2012-12-17 | 2013-03-20 | 江苏龙蟠石化有限公司 | Composite lithium-calcium base lubricating grease and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 1,3,4-噻二唑衍生物的合成及其抗腐减摩性能;刘琳等;《石油化工》;20111031;第40卷(第10期);1089-1093 * |
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