CN108659922A - A kind of graphene lubricating grease and preparation method thereof - Google Patents
A kind of graphene lubricating grease and preparation method thereof Download PDFInfo
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- CN108659922A CN108659922A CN201710194880.4A CN201710194880A CN108659922A CN 108659922 A CN108659922 A CN 108659922A CN 201710194880 A CN201710194880 A CN 201710194880A CN 108659922 A CN108659922 A CN 108659922A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
- C10M2201/0626—Oxides; Hydroxides; Carbonates or bicarbonates used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
- C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2290/00—Mixtures of base materials or thickeners or additives
- C10M2290/04—Synthetic base oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Abstract
The present invention relates to a kind of graphene lubricating grease and preparation method thereof.Novel lubricating grease provided by the invention, on the basis of lubricating grease quality, including following components：35~94.8% lubricating base oil, 5~35% thickening agent, 0.1~15% graphene, 0.1~15% tetralkyl titanate modifying agent.The present invention prepares graphene lubricating grease using one-step method, graphene directly takes part in the forming process of lubricating grease soap fiber with modifying agent, apparent synergistic effect is produced with thickening agent, overcoming the prior art needs the problem of overlength was modified reset time in 6~8 hours, production difficulty is reduced, the batch production in industrialization is conducive to.Prepared lubricating grease is also more excellent in comprehensive performance, and especially antiwear characteristics are greatly improved.
Description
Technical field
The invention belongs to lubricating grease preparation fields, are exactly a kind of novel lubricating grease containing graphene and its preparation
Method.
Background technology
Lubricating grease be it is a kind of by thickening agent, base oil and additive form slave the lubricant of semifluid to solid-like produce
Product are widely used in production and living.Most lubricating grease are used to lubricate, commonly referred to as antifriction grease, in rubbing for machinery
It wipes position to play the role of reducing friction, prevent abrasion, while also having the protective effect for preventing metal erosion and sealing and dustproof concurrently
Effect.There are also lubricating grease to be used exclusively for preventing metal rusting or corrosion, referred to as protects lubricating grease, such as industrial vaseline
Special grease is sealed Deng minority.
In the case of not doping, unsatisfactory, the traditional extreme pressure anti-wear additives of abrasion resistance of most of basis fat
Mostly it is the organic compound of sulfur-bearing, phosphorus, chlorine, molybdenum, lead etc..General chlorine class, sulphur class are used to improve the load resistance ability of lubricating grease, prevent
Only metal surface issues raw burn knot, seizing, scratch in high-load condition, and Phosphorus, organic metal salt is with higher wear-resistant
Ability can effectively prevent or reduce abrasion of metal surface under the conditions of moderate duty.Typically there is dialkyl dithiophosphoric acid
Zinc (ZDDP, code name T202/203) etc., but the additives such as sulphur, phosphorus there are equipment corrode and problem of environmental pollution, in recent years under the pressure of
Environmental protection pressure and actual demand successively have developed the non-traditional extreme pressure anti-wear additives of oxygen-containing, nitrogen, boron etc., while nano material etc.
The continuous development of new technology also causes to emerge in large numbers many new materials, has unique advantage in performance and using upper.
Graphene is a kind of individual layer laminated structure being made of carbon atom, and only there are one the two-dimentional materials of carbon atom thickness
Material, is presently found most thin, maximum intensity, a kind of strongest novel nano-material of electrical and thermal conductivity performance, is referred to as 21 century
" dark fund ", " king of new material ".Graphene has the properties such as excellent heat conduction, conduction, light transmission, and high mechanical strength, quality
Specific surface is big, and when doping shows semiconductor property, in solar cell, stress induction detection, inhales wave stealth material, green catalysis
Equal fields have been widely used.
As the graphene of new material, just show up prominently in the application of traditional technical field of lubricating grease, and most office
It is limited to laboratory research, but application prospect can not despise.Patent CN 104560289 A, CN 104560267 A etc. provide portion
Divide single soap base, compound soap base and polyureas base graphene preparation of greases method；103289802 A of patent CN provide prefabricated
The preparation method of graphene modified lubricating grease；104726186 A of patent CN provide graphene organic silicone oil preparation of greases
Method.But the method that the prior art provides is in the presence of modified reset time length, graphene utilization rate is low, mixes uneven etc. ask
Topic, it is therefore desirable to be further improved graphene preparation of greases method.
Invention content
The present invention provides a kind of novel graphite alkene lubricating grease.
The present invention also provides the novel methods that one-step method prepares graphene lubricating grease, and the method overcome the prior arts to change
Property the problems such as reset time is long, graphene utilization rate is low, mixing is uneven, simplify technological process, can effectively reduce practical work
The cost of industry mass production, and comprehensive performance is more excellent.
Novel graphite alkene lubricating grease provided by the invention, on the basis of lubricating grease quality, including following components：35~
94.8% lubricating base oil, 5~35% thickening agent, 0.1~15% graphene, 0.1~15% tetralkyl titanate
The mass ratio of modifying agent, graphene and modifying agent is 1：0.1~10.
Under preferable case, on the basis of lubricating grease quality, including following components：55~89% lubricating base oil, 10~
25% thickening agent, 0.5~10% graphene, 0.5~10% tetralkyl titanate modifying agent, graphene and modifying agent
Mass ratio is 1：0.2~5.
Base oil used in the present invention can be mineral oil, vegetable oil, synthetic oil or their mixture.Mineral oil is usual
Paraffinic base, cycloalkyl series are selected, vegetable oil can be castor oil, rapeseed oil, peanut oil, soybean oil etc., and synthetic oil can be
Poly-a-olefin oil (PAO), Esters oil, fluorocarbon oil, alkylnaphthalene, ether system synthetic oil etc..
The type covering scope of thickening agent used in the present invention is wider, can be soap base thickening agent, such as lithium soap, calcium soap, sodium
Soap, barium soap, zirconium soap, compound lithium soap, compound soda soap, compound barium soap, calcium complex soap, compound zirconium soap etc.；Can also be that non-soap base is thick
Agent, such as bentonite, silica gel, urea element, polyureas；It can also be that alkyl thickening agent, such as paraffin, ceresine, preferably soap base are thickened
Agent.Thickening agent used can be one or more of above-mentioned thickening agent compounding in lubricating grease, such as polyureas-sulfoacid calcium base, compound
Lithium calcium base etc..Thickening agent quality accounts for the 5~35% of lubricating grease total amount, preferably 10~25%.
Graphene used in the present invention can be commercially available various models, can also be self-control synthesis, method covers chemistry
The Bottom-up graphene methods such as vapor deposition, epitaxial growth, solvent heat and mechanical stripping, solvent stripping, surpass at redox
The Top-down graphene methods such as critical stripping.Graphene quality accounts for the 0.1~15% of lubricating grease total amount, preferably 0.5~
10%, more preferable 2~6%.
Modifying agent used in the present invention is tetralkyl titanate, and alkyl therein can be C1-C5 alkyl, preferably metatitanic acid four
Isopropyl ester and butyl titanate.The mass ratio of graphene and modifying agent is 1：0.1~10, preferably 1：0.2~5, more preferable 1：0.5
~3.
Graphene preparation of greases method provided by the invention includes the following steps：
(1), the aqueous solution of base oil, organic bronsted lowry acids and bases bronsted lowry is first added in fat kettle processed, is warming up to 70~100 DEG C of progress saponification
Reaction；
(2), 100~130 DEG C are continuously heating to, carries out catching up with water；
(3), in step (1) or after step (2), tetralkyl titanate modifying agent and graphene is added, it is fully mixed
It closes；
(4), 180~230 DEG C are continuously heating to, high temperature refining is carried out, then cooling is melted into fat.
In the present invention, the organic acid at least contains higher fatty acids, can also contain small molecule inorganic acid and/or rudimentary
Aliphatic acid and/or aromatic acid.
It is 8-20 that the wherein described higher fatty acids, which is carbon number, the preferably straight chain fatty acid of 10-16 or hydroxy fatty acid, such as
At least one of lauric acid, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxy stearates
Acid.
In the present invention, the molecular weight of the small molecule inorganic acid or lower fatty acid is less than or equal to 150.Wherein, small molecule
Inorganic acid can be selected from least one of boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be with
Selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, decanedioic acid etc., preferably acetic acid and/or
Decanedioic acid.
The aromatic acid can be unitary aromatic acid or binary aromatic acid.Wherein the preferred benzoic acid of unitary aromatic acid, to first
At least one of yl benzoic acid, o-toluic acid and m-methyl benzoic acid, salicylic acid (being septichen).Binary
In the preferred phthalic acid of aromatic acid, M-phthalic acid, terephthalic acid (TPA) and biphenyl dicarboxylic acid (such as 4,4 '-biphenyl dicarboxylic acids)
It is at least one.
The molar ratio of the higher fatty acids and small molecule inorganic acid, lower fatty acid or aromatic acid is 1：0.1-10, more
Preferably 1：0.2-5.
The alkali can be sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, zirconium hydroxide,
Etc..
The features of the present invention is that one-step method prepares graphene lubricating grease, and graphene can be prepared with modifying agent in lubricating grease
Saponification stage, heating catch up with after water and cooling homogenization stage is added one or more times, and graphene and modifying agent
Be added can order in no particular order, can be added, also can be successively added simultaneously together, preferably water caught up with to be added afterwards completely, more preferably
First add partially modified dose in the saponification stage, water is caught up with to add graphene and remaining modifying agent, the modifying agent being first added later
It can account for the 10%~90% of whole modifying agent quality, preferably 30%~60%.
It, as needed can individually or two kinds or more in addition to above-mentioned graphene and modifying agent in the novel lubricating grease of the present invention
Common various grease additives are used in compounding, including extreme pressure anti-wear additives, antirust agent, anti-friction agent, anti emulsifier, oiliness are improved
Agent etc..
Lubricating grease provided by the invention, due to the addition of graphene and modifying agent, with conventional grease various types of properties
While, it may have some properties.Graphene after modified not only has high mechanical strength, good conductivity etc. intrinsic excellent
Point, and oil-soluble is improved, and due to being prepared using one-step method, graphene directly takes part in lubrication with modifying agent
The forming process of fat soap fiber produces apparent synergistic effect with thickening agent.Particularly, if be additionally added before catching up with water
Partially modified dose and graphene, can also generate herbicide interactions, further enhance anti-wear effect, prepared lubricating grease is comprehensive
Can on it is more excellent, be applicable to the harsh operating mode such as high temperature, heavy load, long-time, it is better with other additive compounds,
It can be used for the special occasions such as conduction.
Lubricating grease of the present invention, which overcomes the prior art, needs the problem of overlength was modified reset time in 6~8 hours, reduces production
Difficulty is conducive to the batch production in industrialization.
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
Specific implementation mode
Embodiment 1
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.30kg；Tetraisopropyl titanate 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added 0.30kg tetraisopropyl titanate, mix 10min after be added 0.30kg graphene, be thoroughly mixed, until
Aqueous solution 1.05kg (including 0.15kg lithium hydroxides and the 0.90kg distillations of lithium hydroxide are added when temperature rises to 90 DEG C again
Water).After saponification 15min, continues heat temperature raising and catch up with water, until 200 DEG C, after the refining of the high temperature of 10min, 1.20kg is added
Quench oil be cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lithium base grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxy stearic acids
10 weight % of lithium, 84 weight % of lubricating base oil, 3 weight % of graphene, 3 weight % of tetraisopropyl titanate.
Embodiment 2
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.30kg；Tetraisopropyl titanate 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added lithium hydroxide aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water), saponification
After 15min, continue heat temperature raising and catch up with water, when the completely rear temperature of water being caught up with to rise to 130 DEG C, the tetraisopropyl titanate of 0.30kg is added,
The graphene of 0.30kg is added after mixing 10min, is thoroughly mixed, until temperature rises to 130 DEG C again, continues heating and rises
Temperature, until 200 DEG C, after the refining of the high temperature of 10min, the quench oil that 1.20kg is added is cooled to 80 DEG C.3 are ground by three-roller
It is secondary at fat.Properties of product are as shown in table 1.
In the lithium base grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxy stearic acids
10 weight % of lithium, 84 weight % of lubricating base oil, 3 weight % of graphene, 3 weight % of tetraisopropyl titanate.
Embodiment 3
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.10kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.30kg；Tetraisopropyl titanate 0.60kg.
First 6.90kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when the tetraisopropyl titanate of 0.30kg is added, be thoroughly mixed, until lithium hydroxide is added when rising to 90 DEG C again in temperature
Aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water).After saponification 15min, continue heat temperature raising
Water is caught up with, when the completely rear temperature of water being caught up with to rise to 130 DEG C, the tetraisopropyl titanate of 0.30kg is added, 0.30kg is added after mixing 10min
Graphene, be thoroughly mixed, until temperature rises to 130 DEG C again, continue heat temperature raising, until 200 DEG C, through 10min's
After high temperature refining, the quench oil that 1.20kg is added is cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product such as 1 institute of table
Show.
In the lithium base grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxy stearic acids
10 weight % of lithium, 81 weight % of lubricating base oil, 3 weight % of graphene, 6 weight % of tetraisopropyl titanate.
Embodiment 4
Material component：400SN base oils (100 DEG C of viscosity are 9.32mm2/s) 8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.30kg；Butyl titanate 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added lithium hydroxide aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water), saponification
After 15min, continue heat temperature raising and catch up with water, when the completely rear temperature of water being caught up with to rise to 130 DEG C, the butyl titanate of 0.30kg is added, mixes
The graphene of 0.30kg is added after conjunction 10min, is thoroughly mixed, until temperature rises to 130 DEG C again, continues heat temperature raising,
Until 200 DEG C, after the refining of the high temperature of 10min, the quench oil that 1.20kg is added is cooled to 80 DEG C.It is ground 3 times by three-roller
At fat.Properties of product are as shown in table 1.
In the lithium base grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxy stearic acids
10 weight % of lithium, 84 weight % of lubricating base oil, 3 weight % of graphene, 3 weight % of butyl titanate.
Embodiment 5
Material component：400SN base oils (100 DEG C of viscosity are 9.32mm2/s) 8.40kg；Lithium hydroxide (LiOHH2O)
0.20kg；12- hydroxy stearic acids 0.72kg；Decanedioic acid 0.24kg, tetraisopropyl titanate 0.30kg, graphene 0.30kg.
First 7.20kg base oils, 0.72kg 12- hydroxy stearic acids, 0.24kg decanedioic acid are added in fat kettle processed, heating is stirred
It mixes.Temperature is slowly added to the aqueous solution 1.10kg of lithium hydroxide when rising to 90 DEG C (including 0.20kg lithium hydroxides and 0.90kg steam
Distilled water), after saponification 30min, continue heat temperature raising and catch up with water, catch up with water completely after temperature when rising to 130 DEG C, be added 0.30kg's
Tetraisopropyl titanate mixes the graphene of addition 0.30kg after 10min, is thoroughly mixed, until temperature rises to 130 again
DEG C, continue heat temperature raising, until 200 DEG C, after the refining of the high temperature of 10min, the quench oil that 1.20kg is added is cooled to 80 DEG C.It is logical
It crosses three-roller and grinds 3 times into fat.Properties of product are as shown in table 1.
In the complex lithium grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxyls are hard
7.42 weight % of resin acid lithium, 2.58 weight % of decanedioic acid lithium, 84 weight % of lubricating base oil, 3 weight % of graphene, metatitanic acid four are different
3 weight % of propyl ester.
Embodiment 6
Material component：400SN base oils (100 DEG C of viscosity are 9.32mm2/s) 6.90kg；Calcium hydroxide 0.84kg；Ice vinegar
Sour 1.05kg, 12- hydroxy stearic acid 1.05kg；Tetraisopropyl titanate 0.30kg, graphene 0.30kg.
It first by 6.90kg base oils, 0.65kg calcium hydroxides, 1.30kg distilled water, is added in fat kettle processed, stirs 10min,
Glacial acetic acid 1.05kg is added after mixing, heating is opened after the completion of reaction.The breast of calcium hydroxide is added in temperature when rising to 90 DEG C
After turbid 0.59kg (including 0.19kg calcium hydroxides and 0.40kg distilled water), saponification 30min, continues heat temperature raising and catch up with
Water is added the tetraisopropyl titanate of 0.30kg, is added 0.30kg's after mixing 10min when the completely rear temperature of water being caught up with to rise to 130 DEG C
Graphene is thoroughly mixed, until temperature rises to 130 DEG C again, continues heat temperature raising, until 220 DEG C, the height through 10min
After temperature refining, it is cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the complex calcium lubricating grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxyls are hard
11.17 weight % of resin acid calcium, 13.83 weight % of calcium acetate, 69 weight % of lubricating base oil, 3 weight % of graphene, metatitanic acid four are different
3 weight % of propyl ester.
Embodiment 7
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.10kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.60kg；Tetraisopropyl titanate 0.30kg.
First 6.90kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 80
DEG C when be added lithium hydroxide aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water), saponification
After 15min, continue heat temperature raising and catch up with water, when the completely rear temperature of water being caught up with to rise to 130 DEG C, the tetraisopropyl titanate of 0.30kg is added,
The graphene of 0.60kg is added after mixing 10min, is thoroughly mixed, until temperature rises to 130 DEG C again, continues heating and rises
Temperature, until 200 DEG C, after the refining of the high temperature of 10min, the quench oil that 1.20kg is added is cooled to 80 DEG C.3 are ground by three-roller
It is secondary at fat.Properties of product are as shown in table 1.
In the lithium base grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxy stearic acids
10 weight % of lithium, 81 weight % of lubricating base oil, 6 weight % of graphene, 3 weight % of tetraisopropyl titanate.
Embodiment 8
Material component：400SN base oils (100 DEG C of viscosity are 9.32mm2/s) 6.60kg；Calcium hydroxide 0.84kg；Ice vinegar
Sour 1.05kg, 12- hydroxy stearic acid 1.05kg；Tetraisopropyl titanate 0.60kg, graphene 0.30kg.
It first by 6.60kg base oils, 0.65kg calcium hydroxides, 1.30kg distilled water, is added in fat kettle processed, stirs 10min,
Glacial acetic acid 1.05kg is added after mixing, heating is opened after the completion of reaction.The metatitanic acid of 0.30kg is added in temperature when rising to 90 DEG C
Tetra-isopropyl is thoroughly mixed, until be added when temperature rises to 90 DEG C again calcium hydroxide emulsion 0.59kg (including
0.19kg calcium hydroxides and 0.40kg distilled water), after saponification 30min, continue heat temperature raising and catch up with water, catch up with water completely after temperature
When rising to 130 DEG C, the tetraisopropyl titanate of 0.30kg is added, mixes the graphene of addition 0.30kg after 10min, is sufficiently stirred mixed
It closes, until temperature rises to 130 DEG C again, continues heat temperature raising, until 220 DEG C, after the refining of the high temperature of 10min, it is cooled to 80
℃.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the complex calcium lubricating grease that the present embodiment obtains, on the basis of the weight of lubricating grease, group becomes：12- hydroxyls are hard
11.17 weight % of resin acid calcium, 13.83 weight % of calcium acetate, 66 weight % of lubricating base oil, 3 weight % of graphene, metatitanic acid four are different
6 weight % of propyl ester.
Comparative example 1
This comparative example is not added with graphene and titanate esters modifying agent.
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)9.00kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added lithium hydroxide aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water), saponification
After 15min, continues heat temperature raising and catch up with water, until 200 DEG C, after the refining of the high temperature of 10min, the quench oil cooling of 0.18kg is added
To 80 DEG C.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
Comparative example 2
This comparative example only adds graphene in cooling stage.
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)9.00kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acid 0.98kg, graphene 0.30kg.
The bases 10.00kg lithium base grease is prepared by technique described in comparative example 1, but 0.30kg is added when being cooled to 80 DEG C
Graphene is uniformly mixed.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
Comparative example 3
This comparative example is by titanate esters and graphene and basic fat mechanical mixture
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)9.00kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acid 0.98kg, graphene 0.30kg；Tetraisopropyl titanate 0.30kg.
Prepare 10.00kg bases lithium base grease by technique described in comparative example 1, and with 0.30kg graphenes, 0.30kg titaniums
Sour tetra-isopropyl carries out mechanical mixture, stirs evenly, and 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
Comparative example 4
This comparative example only adds titanate esters before catching up with water, is not added with graphene.
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Tetraisopropyl titanate 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when the tetraisopropyl titanate of 0.30kg is added, the aqueous solution 1.05kg (packets of lithium hydroxide are added when temperature rises to 90 DEG C again
Include 0.15kg lithium hydroxides and 0.90kg distilled water).After saponification 15min, continues heat temperature raising and catch up with water, until 200 DEG C, warp
After the high temperature refining of 10min, the quench oil that 0.18kg is added is cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product
As shown in table 1.
Comparative example 5
This comparative example is catching up with rear completely, water plus titanate esters, is not added with graphene.
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Tetraisopropyl titanate 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added lithium hydroxide aqueous solution 1.05kg (including 0.15kg lithium hydroxides and 0.90kg distilled water), saponification
After 15min, continue heat temperature raising and catch up with water, when the completely rear temperature of water being caught up with to rise to 130 DEG C, the tetraisopropyl titanate of 0.30kg is added,
After temperature rises to 130 DEG C again, continue heat temperature raising, until 200 DEG C, after the refining of the high temperature of 10min, the urgency of 0.18kg is added
Cold oil is cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
Comparative example 6
Tetraisopropyl titanate is replaced with into titanium coupling agent according to method described in patent Example 1.
Material component：(100 DEG C of viscosity are 9.32mm to 400SN base oils2/s)8.40kg；Lithium hydroxide (LiOHH2O)
0.15kg；12- hydroxy stearic acids 0.98kg；Graphene 0.30kg；Titanate coupling agent HC-WT 0.30kg.
First 7.20kg base oils, 0.98kg 12- hydroxy stearic acids are added in fat kettle processed, heating stirring.Temperature rises to 90
DEG C when be added 0.30kg titanate coupling agent HC-WT, mix 10min after be added 0.30kg graphene, be thoroughly mixed,
Until the aqueous solution 1.05kg of lithium hydroxide is added when temperature rises to 90 DEG C again, (including 0.15kg lithium hydroxides and 0.90kg steam
Distilled water).After saponification 15min, continues heat temperature raising and catch up with water, until 200 DEG C, after the refining of the high temperature of 10min, it is added
The quench oil of 0.18kg is cooled to 80 DEG C.3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
Comparative example 7
The graphene being modified with tetraisopropyl titanate is prepared according to method described in 103289802 A embodiments 2 of patent CN
Complex calcium lubricating grease.
Material component：400SN base oils (100 DEG C of viscosity are 9.32mm2/s) 6.60kg；Calcium hydroxide 0.84kg；Ice vinegar
Sour 1.05kg, 12- hydroxy stearic acid 1.05kg；Tetraisopropyl titanate 0.025g, graphene 5.00g.
First 5.00g graphenes are added to containing in 0.025g tetraisopropyl titanates, and appropriate petroleum ether dilution is added,
It is ultrasonically treated 3h under 30 DEG C of temperature conditions, modified graphene powder is made after filtering, drying.
6.90kg base oils, 0.65kg calcium hydroxides, 1.30kg distilled water are added in fat kettle processed, stir 10min, mixes
Glacial acetic acid 1.05kg is added after closing uniformly, heating is opened after the completion of reaction.The breast of calcium hydroxide is added when temperature rises to 90 DEG C
After turbid 0.59kg (including 0.19kg calcium hydroxides and 0.40kg distilled water), saponification 30min, continues heat temperature raising and catch up with
Water, until 220 DEG C, after the refining of the high temperature of 10min, when being cooled to 150 DEG C, the above-mentioned modification of 0.05% (i.e. 5.00g) is added
Graphene grinds 3 times into fat by three-roller.Properties of product are as shown in table 1.
Table 1：PERFORMANCE OF GREASES
By above-mentioned experimental result, comparative example 1,2,3 and comparative example 1, it can be seen that graphene has bright with modifying agent
The effect of aobvious promotion abrasion resistance, the wear scar diameter of graphene lithium base grease drop to 0.40mm or so from 0.83mm, and
Seizing load has been increased to 588N from 98N, and partially modified dose of also certain compound synergistic effect is added outside water forehead catching up with,
Wear scar diameter further drops to 0.30mm；In addition, with graphene complex calcium lubricating grease prepared by technique described in embodiment 3,
Wear scar diameter can further be reduced to 0.22mm.
It can be seen that with 2 by comparative example 1, directly add not modified graphene, do not play the role of wear-resistant；And by right
Ratio 7 in the cooling stage addition of fat processed, also has no it is found that be first modified graphene with a small amount of tetraisopropyl titanate
Apparent anti-wear effect.
It can be seen that by comparative example 3, the modification of unreacted process, directly mix modifying agent, graphene and finished product fat machinery
It closes, also has no wear-resistant effect.
Again by comparative example 4,5 it was determined that graphene has truly had preferable wear-resistant work under the modifying function of titanate esters
With, and the metatitanic acid ester products through hydrolysis also have certain wear-resistant effect, wear scar diameter to drop to 0.50 or so from 0.83,
And seizing load is promoted from 98N to 392N.
It can be seen that by comparative example 5, under conditions of same process, using titanate coupling agent HC-WT modified graphenes,
It having certain effect, wear scar diameter drops to 0.61mm or so from 0.83mm, and seizing load is promoted from 98N to 392N, but
In comparison, it is good to be still not so good as tetralkyl titanate for effect.
Explanation：
1, there are four parameters, i.e. rotating speed, temperature, load, time for the wear-resistant experiment of four-ball tester, this four parameters are to result shadow
Sound is very big, and in standard method SH/T 0204, the rotating speed of standard is 1200r/min, 75 DEG C of temperature, load 392N (namely 40 is public
Jin, 1 kilogram is 98N), 1 hour time.
The test condition of 103289802 A of associated documents CN only gives steel ball model, does not illustrate other parameters,
Do not illustrate, whether using standard method, to only give load 390N, therefore the data of the application and the data of this document are simultaneously
Cannot directly it compare.
Claims (16)
1. a kind of graphene lubricating grease, on the basis of lubricating grease quality, including following components：35~94.8% lubrication base
Oil, 5~35% thickening agent, 0.1~15% graphene, 0.1~15% tetralkyl titanate modifying agent.
2. according to lubricating grease described in claim 1, on the basis of lubricating grease quality, including following components：55~89% lubrication
Base oil, 10~25% thickening agent, 0.5~10% graphene, 0.5~10% tetralkyl titanate modifying agent.
3. according to lubricating grease described in claim 1, wherein the mass ratio of graphene and modifying agent is 1：0.1~10.
4. according to lubricating grease described in claim 1, wherein the thickening agent is selected from soap base thickening agent.
5. according to lubricating grease described in claim 1, wherein the thickening agent is selected from lithium soap, calcium soap, soda soap, barium soap, zirconium soap, answers
Close lithium soap, compound soda soap, compound barium soap, calcium complex soap, compound zirconium soap etc..
6. according to lubricating grease described in claim 1, wherein the modifying agent is tetralkyl titanate, and alkyl therein is C1-C5
Alkyl.
7. a kind of graphene preparation of greases method, includes the following steps：
(1) aqueous solution of base oil, organic bronsted lowry acids and bases bronsted lowry is added in fat kettle processed, is warming up to 70~100 DEG C of progress saponifications；
(2) 100~130 DEG C are continuously heating to, carries out catching up with water；
(3) in the saponification stage of step (1) or after step (2) catches up with water, tetralkyl titanate modifying agent and graphite is added
Alkene is sufficiently mixed；
(4) 180~230 DEG C are continuously heating to, high temperature refining is carried out, then cooling is melted into fat.
8. preparation method according to claim 7, wherein the organic acid is at least containing the higher aliphatic that carbon number is 8-20
Acid.
9. preparation method according to claim 8, wherein the higher fatty acids is selected from lauric acid, palmitic acid, tristearin
At least one of acid, 12- hydroxy stearic acids, eicosyl carboxylic acid.
10. preparation method according to claim 7, wherein the organic acid also contains small molecule inorganic acid and/or rudimentary
Aliphatic acid and/or aromatic acid.
11. preparation method according to claim 10, wherein the molecular weight of the small molecule inorganic acid or lower fatty acid
Less than or equal to 150.
12. preparation method according to claim 11, wherein small molecule inorganic acid in boric acid, phosphoric acid, sulfuric acid extremely
Few a kind of and/or lower fatty acid in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, decanedioic acid at least
One kind and/or aromatic acid are selected from benzoic acid, p-methylbenzoic acid, o-toluic acid and m-methyl benzoic acid, salicylic acid, neighbour
At least one of phthalic acid, M-phthalic acid, terephthalic acid (TPA) and biphenyl dicarboxylic acid.
13. preparation method according to claim 10, wherein the higher fatty acids and small molecule inorganic acid, rudimentary fat
The molar ratio of fat acid or aromatic acid is 1：0.1-10.
14. preparation method according to claim 7, wherein the alkali is selected from sodium hydroxide, potassium hydroxide, hydroxide
At least one of lithium, calcium hydroxide, barium hydroxide, zirconium hydroxide.
15. preparation method according to claim 7, wherein first add partially modified dose in the saponification stage, after catching up with water
Graphene and remaining modifying agent are added, the modifying agent being first added accounts for the 10%~90% of whole modifying agent quality.
16. lubricating grease prepared by one of claim 7-15 the methods.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471510A (en) * | 2019-12-18 | 2020-07-31 | 贵州中时烯材科技有限公司 | Preparation method of graphene composite lubricating grease |
| CN112210421A (en) * | 2020-10-22 | 2021-01-12 | 佛山肯天新材料科技有限公司 | Graphene lubricating grease production process |
| CN116024029A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Lubricating grease and preparation method and application thereof |
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| CN104560264A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Composite lithium-based lubricating grease and preparation method thereof |
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| CN1276412A (en) * | 1999-06-04 | 2000-12-13 | 中国石油化工集团公司 | Process for preparing composite Li-Ca based grease |
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| CN111471510A (en) * | 2019-12-18 | 2020-07-31 | 贵州中时烯材科技有限公司 | Preparation method of graphene composite lubricating grease |
| 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 |
| CN112210421A (en) * | 2020-10-22 | 2021-01-12 | 佛山肯天新材料科技有限公司 | Graphene lubricating grease production process |
| CN116024029A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Lubricating grease and preparation method and application thereof |
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