CN104560313B - A kind of complex lithium-calcium base grease and preparation method thereof - Google Patents
A kind of complex lithium-calcium base grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of complex lithium-calcium base grease and preparation method thereof.On the basis of lubricating grease weight, the complex lithium-calcium base grease includes following components：65 95% lubricating base oil, 5 30% complex lithium-calcium base thickening agent, 0.2 15% graphene.The complex lithium-calcium base grease of the present invention has the performances such as excellent heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life, anticorrosive property and resistance to saltfog.
Description
Technical field
The present invention relates to a kind of lubricant material, is specifically a kind of complex lithium-calcium base grease 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 are to the inoxidizability of lubricating grease, high and low temperature resistance and extreme pressure anti-wear, water resistant
Property, mechanical stability etc. propose increasingly harsher requirement, complex thickener class lubricating grease has obtained very big development.Therefore
There is the document of numerous studies complex lithium-calcium base grease performance.
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 anti-plus water shear stability of product, cryogenic property are not described；CN86103103A discloses one
Footwork prepares the preparation technology of lithium-calcium base grease, obtained product have excellent shear stability and good water-resistance and
Excellent colloid stability, but dropping point is relatively low（180℃）；US5350531 reports a kind of complex lithium-calcium base grease
Preparation method, lubricating grease made from the method has a good mechanical stability, and it is 25 that 100,000 times, which are cut differences, but its dropping point
Less than 200 DEG C；CN1252434A reports a kind of lithium calcium base constituent and its preparation technology, and product has good water resistant shearing
Stability, mechanical stability, resistant of high or low temperature, extreme pressure anti-wear and protective；CN101921649A into system by adding
Surfactant is prepared for a kind of complex lithium-calcium base grease of high dropping point；CN101792689A is replaced with lithium hydroxide suspension
A kind of monohydrate lithium hydroxide, there is provided simple preparation method of high-performance complex lithium-calcium base grease.
In recent years in order to improve the performance of complex lithium-calcium base grease, substantial amounts of research is have also been made in terms of additive,
Such as antioxidant, extreme pressure anti-wear additives, antirust agent etc..Nano material is also gradually available in the application of lubricating grease, such as nanometer titanium dioxide
Silicon, Nano diamond, nano titanium oxide, nano zine oxide etc., but the application still without graphene in lubricating grease so far
Correlative study.
The content of the invention
It is an object of the invention to provide a kind of new complex lithium-calcium base grease and preparation method thereof.
The present inventor has found under study for action, especially adds graphene as a part for thickening agent in initial reaction stage
Enter into base oil and reacted with complex lithium-calcium base thickening agent one, generate the complex lithium-calcium base grease of graphene-containing, it is resulting
Complex lithium-calcium base grease not only there is good electric conductivity, and this method can substantially shorten complex lithium-calcium base lubrication
The preparation time of fat.
An aspect of of the present present invention provides a kind of complex lithium-calcium base grease, on the basis of lubricating grease weight, including it is following
Component：65-95% lubricating base oil, 5-30% complex lithium-calcium base thickening agent, 0.2-15% graphene.
Under preferable case, on the basis of lubricating grease weight, including following components：70-90% lubricating base oil, 8-25%'s
Complex lithium-calcium base thickening agent, 1-10% graphene.
The second aspect of the present invention provides a kind of preparation method of complex lithium-calcium base grease, and this method includes：By stone
Black alkene, complex lithium-calcium base thickening agent and part basis oil are well mixed, refine, cooling, add remaining in 190-240 DEG C of constant temperature
Base oil, necessary additive is added, obtains finished product.
The third aspect of the present invention provides a kind of preparation method of complex lithium-calcium base grease, and this method includes：
By graphene, part basis oil, polymer acid mixing, heating, 80-105 DEG C is warming up to, adds calcium hydroxide and water
Suspension, carry out saponification, then adding low molecular acid and lithium hydroxide into system again carries out saponification, Ran Hou
Refined at 190-240 DEG C, add remaining base oil and be cooled to 100-120 DEG C, add necessary additive afterwards, mill
Into fat, finished product is obtained.
The fourth aspect of the present invention provides complex lithium-calcium base grease made from the above method.
Complex lithium-calcium base grease provided by the invention, there is high dropping point, good mechanical stability, higher anti-oxidant
Property, high-temperature and reversible, preferable pumping, excellent heat endurance, water-resistance and colloid stability, and have with other lubricating grease
Good compatibility.In addition, by the way that preliminary stage of the graphene in fat processed is added so that graphene to be thickened as nucleus
Agent depends on around it structure for forming class micelle, and this synergy between graphene and soap molecule enhances soap molecule and consolidated
Change the ability of base oil, greatly improve into fat speed, shorten saponification time, and enable the fat to be competent in various electricity
Machine, generator, air blower, transportation, the lubrication of iron and steel enterprise and other various industrial equipments, especially suitable for it is various compared with
The lubrication of the friction part of plant equipment under high-temperature wet condition.
Embodiment
An aspect of of the present present invention provides a kind of complex lithium-calcium base grease, on the basis of lubricating grease weight, including it is following
Component：65-95% lubricating base oil, 5-30% complex lithium-calcium base thickening agent, 0.2-15% graphene.
Under preferable case, on the basis of lubricating grease weight, including following components：70-90% lubricating base oil, 8-25%'s
Complex lithium-calcium base thickening agent, 1-10% graphene.
In the complex lithium-calcium base grease of the present invention, the dosage of graphene can be total to larger with complex lithium-calcium thickening agent
It is same to be used as thickening agent, and unconventional conductive agent, one side cause gained complex lithium-calcium base grease to maintain general complex lithium
The advantages of calcium-base grease, such as good colloid stability, high temperatures, low temperature properties, extreme pressure anti-wear, while graphene add
Enter more to improve its oxidation resistance.On the other hand preliminary stage of the graphene in fat processed is added so that greatly improve into
Fat speed, shortens saponification time, so that obtained complex lithium-calcium base grease can be competent in high temperature, high speed, height
The harsh working conditions such as load, more water.
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom, is current most thin but and most in the world
Hard nano material, its thermal conductivity factor is up to 5300W/mK, higher than CNT and diamond, and its resistivity ratio copper or
Silver is lower, for the material that current resistivity in the world is minimum.Because graphene is substantially a kind of transparent, good conductor,
It is adapted to manufacture transparent touch screen, even tabula rasa, solar cell, it is multiple that it is widely used in nanoelectronics, nanometer
The fields such as compound, battery, ultracapacitor, hydrogen storage and biologic applications.
In the present invention, the graphene can be the graphene of existing all size, can also may be used by commercially available
To be obtained by existing various methods.Under preferable case, the graphene is obtained by the method comprised the following steps：
Graphite flakes and sodium nitrate, the concentrated sulfuric acid are well mixed in ice bath, potassium permanganate are slowly added under stirring, in 5-
Stirring reaction at 20 DEG C, 30-45 DEG C of continuation stirring reaction is warming up to, then adds deionized water dilution.Added into system
Hydrogen peroxide solution reduces potassium permanganate, then through pickling, wash, be dried to obtain graphene oxide.By obtained graphene oxide
Be added to the water after carrying out ultrasonication, add hydrazine hydrate, after oil bath reaction fully, obtained black flocculent deposit through washing,
Filter, dry, the powder finally obtained is graphene.The frequency of ultrasonic wave is preferably 20-40kHz.
The graphene obtained using the above method（Referred to as make graphene by oneself）With commercially available graphene in particle diameter distribution, conduction
There is significant advantage in property, stability and dispersiveness, specific performance index see the table below 1.
Table 1
| Commercially available graphene | Make graphene by oneself | |
| Particle diameter, nm | 100~3000 | 80~800 |
| Electrical conductivity, S/cm | 500 | 700-900 |
| Decomposition temperature, DEG C | 410 | 430-480 |
| In 1ml base oils can scattered and non-setting maximum, mg | 5 | 8-12 |
Note：Above-mentioned base oil is base oil used in following embodiments 1, if precipitation is after disperseing in terms of 60 minutes.Above-mentioned grain
Footpath uses dynamic light scattering particle size analyzer Dynapro Titan TC（Producer：Wyatt Technology）Measure.Electrical conductivity
Measured using Bel BEC-950 laboratories resistivity meter.Decomposition temperature uses thermogravimetric analyzer SDT-Q600（Producer：U.S. TA
Instrument companies）Measure.It is same as below.
The complex lithium-calcium base thickening agent of the present invention can be generated by acid and lithium hydroxide and calcium hydroxide reaction, the acid
For polymer acid and the mixed acid of low molecular acid, the polymer acid is the aliphatic acid and/or hydroxyl that carbon number is C12-C25
Aliphatic acid, can be one or more mixtures in laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, it is preferably stearic
Acid and/or 12- hydroxy stearic acids；The low molecular acid can be the dicarboxylic acids that carbon number is 6-10, preferably to benzene two
One or more of mixed acid in formic acid, azelaic acid, decanedioic acid.The mol ratio of polymer acid and low molecular acid is preferably 1:
0.1-1。
Lubricating base oil used in the present invention can be mineral oil, vegetable oil, artificial oil or their mixture, 100 DEG C
Kinematic viscosity is 5-60mm2/ s, preferably 10-30mm2/s.Vegetable oil can be castor oil, rapeseed oil, peanut oil, soya-bean oil etc..Close
Can be poly-a-olefin oil into oil（PAO）, Esters oil, fluorocarbon oil, silicone oil etc..
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its
In, the preferred arylamine kind antioxidant of antioxidant, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, can be diphenylamines,
At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease
The 0.5-12% of gross weight, preferably 0.5-5%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid
At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil
At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
In the present invention, the content of each component is calculated according to inventory in grease composition.Wherein, complex lithium-calcium base
Amount=100% of thickening agent ×（The weight of the weight of the weight of polymer acid calcium+polymer acid lithium+low molecular acid lithium）/ lubricating grease
Gross weight
According to the second aspect of the invention, the invention provides a kind of preparation method of complex lithium-calcium base grease, the party
Method includes：Graphene, complex lithium-calcium base thickening agent and part basis oil is well mixed, refined in 190-240 DEG C of constant temperature, it is cold
But, remaining base oil is added, necessary additive is added, obtains finished product.
Wherein, the dosage of graphene, complex lithium-calcium base thickening agent and base oil causes gained complex lithium-calcium base grease, with
On the basis of lubricating grease weight, including following components：65-95% lubricating base oil, 5-30% complex lithium-calcium base thickening agent, 0.2-
15% graphene.
Under preferable case, the dosage of graphene, complex lithium-calcium base thickening agent and base oil causes gained complex lithium-calcium base profit
Consistent lubricant, on the basis of lubricating grease weight, including following components：70-90% lubricating base oil, 8-25% complex lithium-calcium base thickening
Agent, 1-10% graphene.
According to the third aspect of the invention we, the invention provides a kind of preparation method of complex lithium-calcium base grease, the party
Method includes：
By graphene, part basis oil, polymer acid mixing, heating, 80-105 DEG C is warming up to, adds calcium hydroxide and water
Suspension, carry out saponification, then adding low molecular acid and lithium hydroxide into system again carries out saponification, Ran Hou
Refined at 190-240 DEG C, add remaining base oil and be cooled to 100-120 DEG C, add necessary additive afterwards, mill
Into fat, finished product is obtained.
Graphene, calcium hydroxide, lithium hydroxide, polymer acid, the dosage of low molecular acid and base oil make it that gained is compound
Lithium-calcium base grease, on the basis of lubricating grease weight, including following components：65-95% lubricating base oil, 5-30% complex lithium
Calcium base thickening agent, 0.2-15% graphene.
Under preferable case, graphene, calcium hydroxide, lithium hydroxide, polymer acid, the dosage of low molecular acid and base oil make
Gained complex lithium-calcium base grease is obtained, on the basis of lubricating grease weight, including following components：70-90% lubricating base oil, 8-
25% complex lithium-calcium base thickening agent, 1-10% graphene.
The mol ratio of calcium hydroxide and lithium hydroxide can be 1:1-50, preferably 1:5-20.
Wherein, the temperature for the saponification that polymer acid occurs with calcium hydroxide is preferably 80-105 DEG C, and the time is excellent
Elect 5-30 minutes as.
The temperature for adding the saponification that low molecular acid occurs with lithium hydroxide is preferably 80-105 DEG C, saponification
Time be preferably 5-30 minutes.
In the present invention, the dosage of water is so that saponification can be smoothed out.The water can be all in first time saponification
During reaction in the form of with the suspension of calcium hydroxide and water add, can also part in first time saponification with hydrogen-oxygen
The form for changing the suspension of calcium and water is added, and another part is added in the form of the aqueous solution of lithium hydroxide.
The temperature of the refining is preferably 190-240 DEG C, and the time of refining is preferably 1-25 minutes, more preferably 2-
20 minutes.
By weight, part basis oil is preferably the 50-75% of base oil total amount, and remaining base oil is preferably base oil
The 25-50% of total amount.
The complex lithium-calcium base grease that the preparation method of composite lithium-calcium lubricating grease provided by the invention provides with prior art
Preparation method main difference is that saponification is carried out in the presence of graphene, therefore on other behaviour of the preparation process
Make and condition is referred to prior art progress.
A preferred embodiment of the invention, lubricating grease provided by the invention can be prepared by the following method：
By graphene, 50-75% base oils（In terms of base oil total amount）, polymer acid mixing, heating, be warming up to 80-105
DEG C, the suspension of calcium hydroxide and water is added, saponification 60-240min is carried out, then adds low molecular acid into system again
Saponification 50-240min is carried out with lithium hydroxide aqueous solution, is then refined at 190-240 DEG C, adds remaining base
Plinth oil is cooled to 100-120 DEG C, adds necessary additive such as antioxidant, oiliness improver, tackifier, extreme pressure anti-wear additives etc. afterwards and stirs
Mix uniformly；Fat is milled into, obtains finished product.
Fourth aspect present invention provides the complex lithium-calcium base grease as made from above-mentioned third aspect method.
Compared with the complex lithium-calcium base grease as made from the preparation method that second aspect provides, what fourth aspect provided answers
Closing lithium-calcium base grease has more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear.
In the present invention, the content of each component is calculated according to inventory in grease composition.Wherein, complex lithium-calcium base
Content=100% of thickening agent ×（The weight of the weight of the weight of polymer acid calcium+polymer acid lithium+low molecular acid lithium）/ lubrication
Fat gross weight.
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.Following examples
In, dropping point is measured using GB/T3498 methods, and cone penetration is measured using GB/T269 methods, and oxidation initial temperature uses PDSC side
Method is measured, and Stencil oil-dividing is measured using SH/T0324 methods, and anticorrosive property is measured using GB/T5018 methods, and water leaching number of dropouts is adopted
Measured with SH/T0109 methods, tetra-ball machine test PB is measured using SH/T0202 methods, and tetra-ball machine test PD uses SH/T0202
Method is measured, and copper corrosion performance is measured using GB/T7326 methods, and electric conductivity is measured using SH/T0596 methods, coefficient of friction
Measured using SH/T0847 methods.
Embodiment 1
The preparation of graphene oxide：
1g graphite flakes and 0.5g sodium nitrate are well mixed with the 23ml concentrated sulfuric acids in ice bath, 3g is slowly added under stirring
Potassium permanganate, temperature are maintained at 10 DEG C of 1h stirred below, and then mixture stirs 0.5h at 35 DEG C, then add 50ml deionizations
Water dilutes, during release substantial amounts of heat, enter to exercise temperature in ice bath less than 100 DEG C, add 50ml water, mixture stirring
0.5h, add 200ml deionized waters and further dilute.10ml 30 weight % aqueous hydrogen peroxide solution reduction is added afterwards
Potassium permanganate.Finally, mixture mass concentration is 5% hydrochloric acid（400ml）Washing and filtering, to remove metal ion.Then use
0.5L deionized waters go to deacidify, 60 DEG C of dry 24h, and graphene oxide is made.
The preparation of graphene：
0.1g graphene oxides obtained above are added to ultrasonic disperse in 100ml water（Ultrasonic frequency is 30kHz）
5ml hydrazine hydrates are added after 30min（Mass concentration is 85%）, 100 DEG C of reaction 24h of oil bath, the black flocculent deposit warp finally obtained
Washing, the powder for filtering, being obtained after drying are graphene, and the performance of graphene is as shown in table 2 below.
The preparation of complex lithium-calcium base grease：
Material component：12 grams of graphenes；500SN base oils：712g（100 DEG C of viscosity are 10mm2/s）；Lithium hydroxide monohydrate
11.73g；Calcium hydroxide 4.13g；12- hydroxy stearic acids 48.89g；Decanedioic acid 16.45g；8g antioxidant T501
First 12 grams of graphenes, 475 grams of base oils and 48.89 grams of 12- hydroxy stearic acids are added in fat kettle processed, heating is stirred
Mix, when temperature rises to 80 DEG C, suspension of the addition containing 54.13 grams of calcium hydroxides carries out saponification 0.15h；Add 16.45 grams
Decanedioic acid and the aqueous solution saponification 0.15h containing 11.73 gram of one hydronium(ion) lithia；It is warming up to 190 DEG C of progress high temperature refinings
20min processed；Add 237 grams of base oils and cool to 100 DEG C of additions, 8 grams of antioxidant T501, stir；2 are ground by three-roller
It is secondary into fat.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：The weight of 12- hydroxy stearic acids calcium 2.1
Measure %；The weight % of 12- hydroxy lithium stearates 4.2；The weight % of decanedioic acid lithium 2.2；The weight % of graphene 1.5；The weight of lubricating base oil 89
Measure %；The weight % of antioxidant 1；The mol ratio of calcium hydroxide and lithium hydroxide is 1:5.
Embodiment 2
The preparation of graphene oxide is the same as embodiment 1.
The preparation of graphene：
Graphene oxide made from 0.1g is added to ultrasonic disperse in 100ml water（Ultrasonic frequency is 35kHz）30min
5ml hydrazine hydrates are added afterwards（Mass concentration is 85%）, 100 DEG C of oil bath reaction 24h, the black flocculent deposit finally obtained through washing,
Suction filtration, the powder obtained after drying are graphene, and the performance of graphene is as shown in table 2 below.
The preparation of complex lithium-calcium base grease：
Material component：25.8 gram graphene；150BS base oils：420g（100 DEG C of viscosity are 30mm2/s）；One water hydroxide
Lithium 33.63g；Calcium hydroxide 3.12g；12- hydroxy stearic acids 98.35g；Azelaic acid 46.21g；4.2g di-iso-octyldiphenylamine；
First 25.8 grams of graphenes, 315 grams of base oils and 98.35 grams of 12- hydroxy stearic acids are added in fat kettle processed, heating is stirred
Mix, the suspension progress saponification 0.15h containing 3.12 grams of calcium hydroxide is added when temperature rises to 90 DEG C；Add 46.21 grams of nonyls
Diacid and and the aqueous solution saponification 0.15h containing 33.63 gram of one hydronium(ion) lithia, be warming up to 240 DEG C progress high temperature refinings
2min processed；Add 105 grams of base oils and cool to 110 DEG C of additions, 4.2 grams of di-iso-octyldiphenylamines, stir；Pass through three-roller
3 times are ground into fat.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：The weight of 12- hydroxy stearic acids calcium 2.2
Measure %；The weight % of 12- hydroxy lithium stearates 14.6；The weight % of azelaic acid lithium 8.2；The weight % of graphene 4.3；The weight of lubricating base oil 70
Measure %；The weight % of antioxidant 0.7；The mol ratio of calcium hydroxide and lithium hydroxide is 1:19.
Embodiment 3
The preparation of graphene oxide is the same as embodiment 1.
The preparation of graphene：
Graphene oxide made from 0.1g is added to ultrasonic disperse in 100ml water（Ultrasonic frequency is 40kHz）30min
5ml hydrazine hydrates are added afterwards（Mass concentration is 85%）, 100 DEG C of oil bath reaction 24h, the black flocculent deposit finally obtained through washing,
Suction filtration, the powder obtained after drying are graphene, and the performance of graphene is as shown in table 2 below.
The preparation of complex lithium-calcium base grease：
Material component：58.8 gram graphene；PAO6 synthetic hydrocarbon oils：450g（100 DEG C of viscosity are 5.8mm2/s）；One water hydrogen-oxygen
Change lithium 16.59g；Calcium hydroxide 3.25g；12- hydroxy stearic acids 60.60g；Terephthalic acid (TPA) 14.16g；1.2g phenyl-α-naphthalene
Amine；
First 58.8 grams of graphenes, 230 grams of base oils and 60.60 grams of 12- hydroxy stearic acids are added in fat kettle processed, heating is stirred
Mix, the suspension progress saponification 0.15h containing 3.25 grams of calcium hydroxide is added when temperature rises to 100 DEG C；14.16 grams of addition is right
Phthalic acid and the aqueous solution saponification 0.15h containing 16.59 gram of one hydronium(ion) lithia, it is warming up to 210 DEG C of progress high temperature
Refine 10min；Add 220 grams of base oils and cool to 120 DEG C of addition 1.2g phenyl-α-naphthylamines, stir；Ground by three-roller
2 times are ground into fat.Properties of product are as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：The weight % of calcium stearate 2.16；Firmly
The weight % of resin acid lithium 10.31；The weight % of terephthalic acid (TPA) lithium 2.53；The weight % of graphene 9.8；The weight % of lubricating base oil 75；Antioxygen
The weight % of agent 0.2；The mol ratio of calcium hydroxide and lithium hydroxide is 1:9.
Embodiment 4
The preparation of graphene oxide is the same as embodiment 1.
The preparation of graphene：
Graphene oxide made from 0.1g is added to ultrasonic disperse in 100ml water（Ultrasonic frequency is 25kHz）30min
5ml hydrazine hydrates are added afterwards（Mass concentration is 85%）, 100 DEG C of oil bath reaction 24h, the black flocculent deposit finally obtained through washing,
Suction filtration, the powder obtained after drying are graphene, and the performance of graphene is as shown in table 2 below.
The preparation of complex lithium-calcium base grease：
Material component：52 grams of graphenes；500SN and 150BS miscella：584g（100 DEG C of viscosity are 13mm2/s）；One
Water lithium hydroxide 30.89g；Calcium hydroxide 4.54g；12- hydroxy stearic acids 103.7g；Decanedioic acid 38.24g；4g antioxidant T501；
First by 52 grams of graphenes, 439 grams of base oils and 103.7 grams of 12- hydroxy stearic acids and addition fat kettle, heating stirring, work as temperature
Degree rises to 95 DEG C and adds the suspension progress saponification 0.15h containing 3.25 grams of calcium hydroxide, adds 38.24 grams of decanedioic acid and contains
There is the aqueous solution saponification 0.15h of 30.89 gram of one hydronium(ion) lithia, be warming up to 200 DEG C and carry out high temperature refining 8min；Add
145 grams of base oils cool to 120 DEG C of additions, 4 grams of antioxidant T501, stir；2-3 times is ground into fat by three-roller.Product
Performance is as shown in table 3.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：The weight % of calcium stearate 2.26；Firmly
The weight % of resin acid lithium 12.96；The weight % of decanedioic acid lithium 4.78；The weight % of graphene 6.5；The weight % of lubricating base oil 73；Antioxidant 0.5
Weight %；The mol ratio of calcium hydroxide and lithium hydroxide is 1:12.
Comparative example 1
Material component：In addition to not graphene-containing, remaining is the same as embodiment 4
Method according to embodiment 4 prepares complex lithium-calcium base grease, unlike, the preparation of complex lithium-calcium base grease
During be added without graphene.The performance of complex lithium-calcium base grease product is as shown in table 3.
Comparative example 2
Raw material components are the same as embodiment 4
Method according to embodiment 4 prepares complex lithium-calcium base grease, unlike, whole graphenes are with antioxidant T501
Add together.The performance of complex lithium-calcium base grease product is as shown in table 3.
Comparative example 3
Method according to embodiment 4 prepares complex lithium-calcium base grease, unlike, graphene by identical weight scale
Graphite replaces.The performance of complex lithium-calcium base grease product is as shown in table 3.
Embodiment 5
The preparation of graphene is the same as embodiment 1
Material component：With embodiment 4
First by 439 grams of base oils and 103.7 grams of stearic acid and addition fat kettle, heating stirring, when temperature rises to 95 DEG C
Add the suspension containing 3.25 grams of calcium hydroxides and carry out saponification 0.15h, add 38.24 grams of decanedioic acid and contain 30.89 grams
The aqueous solution saponification 0.15h of one hydronium(ion) lithia, then add 52 grams of graphenes into system and be warming up to 200 DEG C of progress height
Temperature refining 8min；Add 145 grams of base oils and cool to 120 DEG C of additions, 4 grams of antioxidant T501, stir；Ground by three-roller
2-3 times is ground into fat.Properties of product are as shown in table 3.
Embodiment 6
Method according to embodiment 4 prepares complex lithium-calcium base grease, unlike, graphene use is commercially available from Bei Jingji
The model specification of An Xin science and trade Co., Ltd is G20 graphene product（Purity>95%, graphene size 100-
200nm）, gained grease product performance is as shown in table 3.
Table 2
Table 3：PERFORMANCE OF GREASES
Can be seen that complex lithium-calcium base grease of the invention from the result of above-mentioned table 3 has excellent heat-resisting quantity, resists
The performances such as water-based and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life, anticorrosive property and resistance to saltfog.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
- A kind of 1. complex lithium-calcium base grease, it is characterised in that on the basis of lubricating grease weight, including following components：65-95% Lubricating base oil, 5-30% complex lithium-calcium base thickening agent, 0.2-15% graphene, the system of the complex lithium-calcium base grease Preparation Method includes：By graphene, part basis oil mix with polymer acid, heat, be warming up to 80-105 DEG C, addition calcium hydroxide With the suspension of water, saponification is carried out, low molecular acid is added afterwards and lithium hydroxide carries out saponification, then in 190- Refined at 240 DEG C, add remaining base oil and be cooled to 100-120 DEG C, add necessary additive afterwards, be milled into Fat, obtain finished product；Wherein described polymer acid is the aliphatic acid and/or hydroxy fatty acid that carbon number is C12-C25, described low Molecule acid is the dicarboxylic acids that carbon number is C6-C10.
- 2. complex lithium-calcium base grease according to claim 1, wherein, on the basis of lubricating grease weight, including with the following group Point：70-90% lubricating base oil, 8-25% complex lithium-calcium base thickening agent, 1-10% graphene.
- 3. complex lithium-calcium base grease according to claim 1 or 2, wherein, the graphene can in 1ml base oils Scattered and non-setting maximum is 8-12mg.
- 4. complex lithium-calcium base grease according to claim 1 or 2, wherein, the particle diameter of the graphene is 80-800nm, Electrical conductivity is 700-900S/cm, and decomposition temperature is 430-480 DEG C.
- 5. complex lithium-calcium base grease according to claim 1 or 2, wherein, the institute that polymer acid occurs with calcium hydroxide The temperature for stating saponification is 80-105 DEG C, and the time of saponification is 5-30 minutes；Low molecular acid is added to send out with lithium hydroxide The temperature of the raw saponification is 80-105 DEG C, and the time of saponification is 5-30 minutes.
- 6. complex lithium-calcium base grease according to claim 1 or 2, wherein, the polymer acid and low molecular acid rub You are than being 1:0.1-1.
- 7. complex lithium-calcium base grease according to claim 1 or 2, wherein, the polymer acid is laurate, palm One or more in acid, stearic acid, 12- hydroxy stearic acids；The low molecular acid is terephthalic acid (TPA), azelaic acid, decanedioic acid In one or more.
- 8. complex lithium-calcium base grease according to claim 1 or 2, wherein, the mol ratio of calcium hydroxide and lithium hydroxide For 1:1-50.
- 9. complex lithium-calcium base grease according to claim 1 or 2, wherein, the mol ratio of calcium hydroxide and lithium hydroxide For 1:5-20.
- 10. complex lithium-calcium base grease according to claim 1 or 2, wherein, 100 DEG C of motions of the lubricating base oil Viscosity is 5-60mm2/s。
- 11. complex lithium-calcium base grease according to claim 1 or 2, wherein, the complex lithium-calcium base grease also contains 0.5-15 weight % additive.
- 12. a kind of preparation method of complex lithium-calcium base grease, this method include：By graphene, part basis oil mix with polymer acid, heat, be warming up to 80-105 DEG C, addition calcium hydroxide and water Suspension, saponification is carried out, add low molecular acid afterwards and lithium hydroxide carries out saponification, then at 190-240 DEG C Refined, add remaining base oil and be cooled to 100-120 DEG C, add necessary additive afterwards, be milled into fat, obtain into Product；Wherein described polymer acid is the aliphatic acid and/or hydroxy fatty acid that carbon number is C12-C25, and the low molecular acid is Carbon number is C6-C10 dicarboxylic acids；Graphene, calcium hydroxide, lithium hydroxide, polymer acid, the dosage of low molecular acid and base oil cause gained complex lithium-calcium Base grease, on the basis of lubricating grease weight, including following components：65-95% lubricating base oil, 5-30% complex lithium-calcium Base thickening agent, 0.2-15% graphene.
- 13. preparation method according to claim 12, wherein, the saponification that polymer acid occurs with calcium hydroxide Temperature be 80-105 DEG C, the time of saponification is 5-30 minutes；Add the soap that low molecular acid occurs with lithium hydroxide The temperature for changing reaction is 80-105 DEG C, and the time of saponification is 5-30 minutes.
- 14. the preparation method according to claim 12 or 13, wherein, the graphene can disperse in 1ml base oils And non-setting maximum is 8-12mg.
- 15. the preparation method according to claim 12 or 13, wherein, the particle diameter of the graphene is 80-800nm, conductance Rate is 700-900S/cm, and decomposition temperature is 430-480 DEG C.
- 16. the preparation method according to claim 12 or 13, wherein, the mol ratio of calcium hydroxide and lithium hydroxide is 1:1- 50；The mol ratio of the polymer acid and low molecular acid is 1：0.1-1.
- 17. preparation method according to claim 16, wherein, the mol ratio of calcium hydroxide and lithium hydroxide is 1:5-20.
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| CN105199818A (en) * | 2015-10-23 | 2015-12-30 | 中国石油化工股份有限公司 | Lubricating grease composition special for washer suspender and preparation method thereof |
| CN106635262B (en) * | 2016-12-06 | 2019-12-03 | 路伯润滑油（苏州）有限公司 | A kind of Lubricating Grease for Speed Reducer and preparation method thereof |
| CN106635348A (en) * | 2016-12-08 | 2017-05-10 | 新乡市恒星科技有限责任公司 | Marine propeller lubricating grease and preparation method thereof |
| CN109097177A (en) * | 2018-09-03 | 2018-12-28 | 郑州市欧普士科技有限公司 | A kind of nano-graphene cement rotary kiln exposed gear grease and preparation method thereof |
| CN111471510B (en) * | 2019-12-18 | 2022-03-29 | 贵州中时烯材科技有限公司 | Preparation method of graphene composite lubricating grease |
| CN116814317A (en) * | 2023-05-26 | 2023-09-29 | 新乡市恒星科技有限责任公司 | Special lubricating grease for high-temperature-resistant conductive bearing and preparation method thereof |
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| CN101792689A (en) * | 2010-02-03 | 2010-08-04 | 上海禾泰特种润滑技术有限公司 | High-performance complex lithium-calcium base grease composition and method for preparing same |
| 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 |
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| CN101792689A (en) * | 2010-02-03 | 2010-08-04 | 上海禾泰特种润滑技术有限公司 | High-performance complex lithium-calcium base grease composition and method for preparing same |
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