CN104560265B

CN104560265B - A kind of polyurea grease and preparation method thereof

Info

Publication number: CN104560265B
Application number: CN201310516334.XA
Authority: CN
Inventors: 孙洪伟; 么佳耀; 郑会; 何懿峰; 段庆华; 张建荣; 陈政; 刘中其; 姜靓
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Beijing General Fine Chemical Technology Development Co ltd; Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-28
Filing date: 2013-10-28
Publication date: 2018-04-13
Anticipated expiration: 2033-10-28
Also published as: CN104560265A

Abstract

The invention discloses a kind of polyurea grease, it is characterised in that on the basis of lubricating grease weight, including following components：The graphene of 0.2 15 weight %；The polyurea compound of 4 30 weight %；The additive of the base oil of 65 95 weight % and 0.5 15 weight %.The invention also discloses the preparation method of polyurea grease and its polyurea grease of preparation.The polyurea grease of the present invention, not only with excellent anticorrosive property and resistance to saltfog, but also with the performance such as excellent heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, and longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stablized.

Description

A kind of polyurea grease and preparation method thereof

Technical field

The present invention relates to lubricating grease, and in particular, to a kind of polyurea grease and preparation method thereof.

Background technology

Urea-base grease is to be thickened mineral oil or artificial oil by organic compound urea and obtained, thickening agent not metal ion, The catalytic action that metal ion aoxidizes base oil is avoided, urea-base grease has good oxidation stability, thermostability And other various excellent performances, also there is especially long service life, be a kind of multipurpose grease, various lubricating grease can be prepared Meet different requirements, be used in high temperature, low temperature, high load capacity, wide velocity interval and the occasion contacted with impedance dielectric, extensively It is general to be applied to the industries such as electric appliance, metallurgy, food, automobile, papermaking.

Have the performance that a large amount of patents inquire into two urea greases in recent years, such as US5158694 by diisocyanate and water and Amine reaction prepares polyurea grease, but the dropping point of its product is between 230-260 DEG C；Presence of the CN1272530A in base oil Under, make C8-C24 fatty amines and excessive di-isocyanate reaction, neutralized unreacted diisocyanate with water, the reaction was continued It it is 130-200 DEG C to temperature, two urea grease dropping points prepared by this method reach 260-330 DEG C；CN1580211A by organic amine and Isocyanates is mixed and reacted, and after temperature of charge is increased to 100-150 DEG C, adding quench oil makes material cool down rapidly, grinds Into fat, urea-base grease prepared by this method has stable vibration values；CN1408825A is at 50-120 DEG C by base oil, alkylamine Mix, reacted with excessive diisocyanate, add in excessive water with unreacted diisocyanate, be warming up to melting, Quench oil is added, kettle is cooled down out and obtains the lubricating grease of appearance transparent；CN101368129A adds borate into system Extreme pressure anti-wear additives, improve the comprehensive performance of lubricating grease, reduce cost；CN1657599A in polyurea grease by adding Calcium containing compound improves the oxidation stability of lubricating grease, its complex process.CN101111591A refer to four urea greases, but It is that preparation process is more complicated, and also introduces metal ion, this will influences the oxidation stability of polyurea grease； CN101693851A using two ureas, triuret, four ureas mixture and introduce fat made from amidic-salt thickening agent there is excellent height Warm nature energy, resistance leachability, good extreme pressure anti-wear；Thickening agent used in CN1056313A is two ureas and four urea mixtures, the fat Excellent performance is had more in the machinery operated for a long time.

In recent years in order to improve two urea greases, four urea greases, Hexaurea lubricating grease and the performance of eight urea greases, adding It has also been made substantial amounts of research, such as antioxidant, extreme pressure anti-wear additives, antirust agent etc. in terms of adding agent.Nano material is also gradually available for In the application of lubricating grease, such as nano silicon dioxide, Nano diamond, nano-titanium dioxide, nano zine oxide, but do not have still so far There is the correlative study of application of the graphene in lubricating grease.

The content of the invention

The object of the present invention is to provide a kind of polyurea grease of graphene-containing and preparation method thereof.

The present inventor has found under study for action, is added to graphene as a part for thickening agent in initial reaction stage In base oil, the polyurea grease for the generation graphene-containing that reacts with polyurea thickening agent one, obtained polyurea grease is not only With good electric conductivity, and this method can be obviously shortened the preparation time of polyurea grease.

Therefore, on the one hand, the present invention provides a kind of polyurea grease, it is characterised in that on the basis of lubricating grease weight, Including following components：The graphene of 0.2-15 weight %；The polyurea compound of 4-30 weight %；The base oil of 65-95 weight %.

Preferably, on the basis of lubricating grease weight, including following components：The graphene of 1-10 weight %；6-25 weight %'s Polyurea compound；The base oil of 70-93 weight %.

Second aspect, the present invention provides the preparation method of polyurea grease as described above, it is characterised in that this method Including：Graphene, polyurea compound and part basis oil are uniformly mixed, refined in 180-230 DEG C of constant temperature, cooling, more than addition Base oil is measured, necessary additive is added, obtains finished product.

The third aspect, the present invention provides a kind of preparation method of polyurea grease, it is characterised in that this method includes：

（1）By part graphene, organic amine and part basis oil Hybrid Heating, heating treats that organic amine melts completely；

（2）Diisocyanate, remainder graphene and part basis oil Hybrid Heating are made into its thawing；

（3）By step（1）And step（2）Gained mixed solution is mixed and reacted, and is then warming up to 180-230 DEG C of perseverance Temperature refining, cooling, adds surplus base oil, adds necessary additive, obtain finished product.

Fourth aspect, the present invention provides a kind of preparation method of polyurea grease, it is characterised in that this method includes：

（1）By part graphene, diisocyanate and part basis oil Hybrid Heating to 50-60 DEG C, diamines, heating are added To 80-100 DEG C, react 10-60 minutes；

（2）By monoamine, remainder graphene and part basis oil Hybrid Heating to 50-60 DEG C；

5th aspect, the present invention provides a kind of preparation method of polyurea grease, it is characterised in that this method includes：

（1）By part graphene, diisocyanate and part basis oil Hybrid Heating to 50-70 DEG C；

（2）By monoamine, remainder graphene and part basis oil Hybrid Heating to 50-70 DEG C；

（3）By step（1）And step（2）Gained mixed solution, which is mixed and heated up, to be reacted, and then adds diamines, reaction 10-60 minutes；

（4）Step is added to after the oily and remaining diisocyanate of part basis is heated to 50-70 DEG C（3）Products therefrom In, to be reacted 10-60 minutes at 80-100 DEG C, continue to be warming up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, Necessary additive is added, obtains finished product.

6th aspect, the present invention provides a kind of preparation method of polyurea grease, it is characterised in that this method includes：

（1）By part graphene, diisocyanate and part basis oil Hybrid Heating to 50-70 DEG C, diamines heating is added Reacted 20-60 minutes to 80-90 DEG C, be slowly added to diamines again, reacted 10-60 minutes at 80-90 DEG C；

（3）By step（1）And step（2）Gained mixed solution, which is mixed and is warming up at 80-90 DEG C, to react 10-60 minutes, Continue to be warming up to 180-220 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.

7th aspect, the present invention provides the polyurea grease as made from method as described above.

The polyurea grease that the present invention synthesizes has the advantages that general urea-base grease, such as good colloid stability, height Warm nature, low temperature properties, extreme pressure anti-wear etc., while the addition of graphene more improves its oxidation resistance.And since graphene exists The preliminary stage of fat processed adds so that greatly improves into fat speed, shortens saponification time, so that obtained polyureas Lubricating grease can be competent in the harsh working condition such as high temperature, high speed, high load capacity, more water.Trace it to its cause, it may be possible to because in fat processed The graphene that preliminary stage adds causes thickening agent to depend on the structure of formation class micelle around it, graphene and soap as nucleus This synergistic effect between molecule enhances the ability of the molecules immobilized base oil of soap.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

On the one hand, the present invention provides a kind of polyurea grease, on the basis of the polyurea grease weight, including with the following group Point：The graphene of 0.2-15 weight %；The polyurea compound of 4-30 weight %；The base oil of 65-95 weight %.

In the polyurea grease of the present invention, the dosage of graphene is larger, with polyureas collectively as thickening agent, and it is unconventional Conductive agent, on the one hand so that gained polyurea grease the advantages of maintaining general urea-base grease, such as good colloid are stabilized Property, high temperatures, low temperature properties, extreme pressure anti-wear etc., while the addition of graphene more improves its oxidation resistance.On the other hand by Added in graphene in the preliminary stage of fat processed so that fat speed is greatly improved into, shortens saponification time, so that Obtained polyurea grease can be competent in the harsh working condition such as high temperature, high speed, high load capacity, more water.

Graphene is a kind of new material for the individual layer laminated structure being made of carbon atom, be it is current it is most thin in the world be but also most Hard nano material, its thermal conductivity factor is up to 5300W/mK, higher than carbon nanotubes and diamond, and its resistivity ratio copper or Silver is lower, for the material of current resistivity minimum in the world.Since graphene is substantially a kind of transparent, good conductor, Manufacture transparent touch screen, even tabula rasa, solar cell are adapted to, 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 various specifications, can be commercially available, also may be used To be obtained by existing various methods.Under preferable case, the graphene is obtained by method comprising the following steps：

Graphite flakes and sodium nitrate, the concentrated sulfuric acid are uniformly mixed in ice bath, potassium permanganate are slowly added under stirring, 10 Reaction is stirred at DEG C, 35 DEG C is warming up to and continues stirring reaction, then add deionized water dilution.Hydrogen peroxide is added into system Solution reduction potassium permanganate, then through pickling, wash, be dried to obtain graphene oxide.Obtained graphene oxide is added into water After middle ultrasonic wave, hydrazine hydrate is added, after oil bath reaction fully, obtained black flocculent deposit is through washing, filtering, dry, finally Obtained powder is graphene.

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 Bell BEC-950 laboratories resistivity meter.Decomposition temperature uses thermogravimetric analyzer SDT-Q600（Producer：U.S. TA Instrument companies）Measure.It is same as below.

In the present invention, the polyurea compound can be polyurea compound commonly used in the art without particular/special requirement, such as can Think at least one of two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein dimerization Carbamide compound, four polyurea compounds, six polyurea compounds, the weight ratio of eight polyurea compounds can be arbitrary proportion.More preferably The polyurea compound is two polyurea compounds.

In the present invention, two polyurea compound preferably has with lower structure：

Wherein, two R¹It can be the same or different, can be each alkyl, cycloalkyl or aryl, alkyl or cycloalkanes The carbon number of base can be 8-24, be preferably 10-18, and aryl can be phenyl or substituted phenyl, be preferably phenyl or C1-C3 alkane Base or the phenyl of halogen substitution.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, be preferably 6-20, R³More preferably

In At least one.

In the present invention, four polyurea compound preferably has with lower structure：

Wherein, R¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10- 18, aryl can be phenyl or substituted phenyl, be preferably phenyl or the phenyl of C1-C3 alkyl or halogen substitution.

Wherein, R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, be preferably 2-8, arlydene can To be phenylene or biphenylene.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub- cycloalkanes

The carbon number of base can be 6-30, be preferably 6-20, R³More preferably

In At least one.

In the present invention, six polyurea compound preferably has with lower structure：

Wherein, R¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10- 18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, be preferably 6-20, R³More preferably In At least one.

In the present invention, eight polyurea compound preferably has with lower structure：

Wherein, R¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, be preferably 10- 18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.

Above-mentioned polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be by It is prepared according to CN103060069A, CN103060070A, CN103060068A, CN103060067A method recorded.

The lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of movements are glutinous Spend for 5-60mm²/ s, more preferably 10-30mm²/s.Artificial oil can be poly-a-olefin oil（PAO）, Esters oil, alkyl-silicone oil, take Hold in the palm artificial 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, accounts 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 0.8-8%, 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.

Second aspect, the present invention provides the preparation method of polyurea grease as described above, this method includes：By graphite Alkene, polyurea compound and part basis oil are uniformly mixed, and are refined in 180-230 DEG C of constant temperature, cooling, adds surplus base oil, add Enter necessary additive, obtain finished product.

In the present invention, for graphene, polyurea compound and base oil as described above, details are not described herein.

It will be understood by those skilled in the art that the amount of part basis oil and the sum of the amount of surplus base oil are as used Base oil total amount, in the present invention, part basis oil and the weight ratio of surplus base oil are preferably 1：0.1-0.5.

The third aspect, the preparation method the present invention provides polyurea compound for the polyurea grease of two polyureas, this method Including：

Relative to the graphene of 2kg, the dosage of lube base oil is preferably 60-65kg.

Fourth aspect, the present invention provides prepare polyurea compound be four polyureas polyurea grease preparation method, its It is characterized in that, this method includes：

5th aspect, the preparation method the present invention provides polyurea compound for the polyurea grease of six polyureas, its feature It is, this method includes：

6th aspect, the preparation method the present invention provides polyurea compound for the polyurea grease of eight polyureas, its feature It is, this method includes：

When the polyurea compound is four polyurea compounds, six polyurea compounds or eight polyurea compounds, relative to 15g Graphene, the dosage of lube base oil is preferably 620-680g.

It will be understood by those skilled in the art that the sum of amount of part basis oil used in each step is base used The total amount of plinth oil.Wherein, the preparation method for polyurea compound for the polyurea grease of two polyureas, four polyureas or eight polyureas, Step（1）The amount and step of part basis oil used（2）Part basis oil used and step（3）The weight of surplus base oil used Than being preferably 1：0.1-1：0.1-1.Preparation method for polyurea compound for the polyurea grease of six polyureas, step（1）Institute With the amount and step of part basis oil（2）Part basis oil used and step（4）The weight ratio of surplus base oil used is preferably 1：0.1-1：0.1-1.

The organic amine can be monoamine or diamine, or both add monoamine, be additionally added diamines, with step（2） The diisocyanate of addition is reacted, and is in step（3）Polyurea compound is prepared in products therefrom, it is poly- that mixing can be prepared Urea, can also prepare single two polyurea compound, four polyurea compounds, six polyurea compounds or eight polyurea compounds.

The method of mixing polyureas is prepared without particular/special requirement, the thinkable various sides of those skilled in the art institute can be used Method, it is for instance possible to use the method for United States Patent (USP) US3243372.

In the present invention, step can be included in by preparing the method for the polyurea grease that polyurea compound is two polyurea compounds Suddenly（1）Middle addition part graphene, part basis oil and monoamine, stir 2-8 minutes, add and be dissolved in another part base oil In diisocyanate and remainder graphene, stir 2-8 minute, the molar ratio of diisocyanate and monoamine is 1:2.Then 180-230 DEG C of constant temperature refining is warming up to, cooling, adds surplus base oil, add necessary additive, obtain finished product.

In the present invention, step can be included in by preparing the method for the polyurea grease that polyurea compound is four polyurea compounds Suddenly（1）Middle addition part graphene, base oil, stir evenly, add diamines, stir 2-8 minutes, add monoamine, 2-8 points of stirring Clock, adds the diisocyanate being dissolved in another part base oil and remainder graphene, diisocyanate, diamines with The molar ratio of monoamine is 2:1:2.Then 180-230 DEG C of constant temperature refining is warming up to, cooling, adds surplus base oil, adds necessary Additive, obtain finished product.

In the present invention, prepare polyurea compound be six polyurea compounds method can include add part basis oil and Graphene, stirs evenly, and adds monoamine, stirs 2-8 minutes, adds diamines, stirs 2-8 minutes, adds dissolved with two isocyanides Another part base oil of acid esters and remaining graphene, stirs 2-8 minute, successively added diisocyanate, monoamine, diamines and The molar ratio of diisocyanate is 2:2:2:1.Then 180-230 DEG C of constant temperature refining is warming up to, cooling, adds surplus base oil, Necessary additive is added, obtains finished product.

In the present invention, prepare polyurea compound be eight polyurea compounds method can include add part basis oil and Graphene, stirs evenly, and adds diamines, stirs 2-8 minutes, adds diamines again, stirs 2-8 minutes, adds monoamine, stirs 2- 8 minutes, another part base oil dissolved with diisocyanate and remainder graphene is then added, added two is different successively Cyanate, diamines, the molar ratio of diamines and monoamine are 4:2:1:2.Then 180-230 DEG C of constant temperature refining is warming up to, cooling, adds Enter surplus base oil, add necessary additive, obtain finished product.

The diisocyanate ester structure is OCN-R³- NCO, R³Can be that carbon number is 6-30, the preferably arlydene of 6-20, Asia Alkyl or cycloalkylidene, are preferably Deng. For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- Asias Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng At least one of.

The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R¹-NH₂, R therein¹Can be alkyl, ring Alkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, and aryl can be phenyl or substituted phenyl, It is preferred that phenyl or the phenyl of C1-C3 alkyl or halogen substitution.It is preferred that the monoamine is fatty amine and the mixture of arylamine, and the two Molar ratio be 0.5-2:1.The arylamine is preferably the arylamine of aniline, m-chloroaniline, parachloroanilinum, para-totuidine, the fat Fat amine is preferably selected from the fatty amine of lauryl amine, tetradecy lamine, cetylamine, octadecylamine.

The diamines can be fatty amine or arylamine, structural formula NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferable diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4- benzidines aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6- oneself two The straight-chain fatty amine of amine.

For refining process, preferably first 180-230 DEG C of constant temperature 5- is finally warming up in 100-120 DEG C of constant temperature 10-20 minutes 20 minutes；150-160 DEG C is cooled to, surplus base oil is added, treats that temperature is cooled to 100-120 DEG C, add necessary additive, Stirring, circulating filtration, homogenizing, degassing.

In the present invention, part graphene and the weight ratio of remainder graphene are preferably 1：0.1-10, further preferably For 1：0.5-5.

According to the present invention, the dosage of graphene, diisocyanate, various amine and base oil to lubricate with obtained polyureas On the basis of fat weight, the content of graphene is 0.2-15 weight %, is preferably 1-10 weight %；The content of polyurea compound is 4-30 Weight %, is preferably 6-25 weight %；The content of base oil is 65-95 weight %, is preferably 70-93 weight %.

For the polyurea grease obtained using the above method, wherein the content of polyurea compound is according to the isocyanic acid to feed intake The weight of ester and amine polyurea compound that gained obtains in theory is calculated.The content of graphene is according to inventory come really It is fixed.

Compared with the polyurea grease as made from the preparation method that second aspect provides, the polyureas that the 7th aspect provides lubricates Fat has more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear.

The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.Following embodiments In, dropping point is measured using GB/T3498 methods, and cone penetration is measured using GB/T269 methods, and oxidation stability uses SH/T0325 Method measures, and Stencil oil-dividing is measured using SH/T0324 methods, and anticorrosive property is measured using GB/T5018 methods, water leaching number of dropouts Measured using SH/T0109 methods, tetra-ball machine test PB is measured using SH/T0202 methods, and tetra-ball machine test PD uses SH/ T0202 methods measure, and copper corrosion performance is measured using GB/T7326 methods, and electric conductivity is measured using SH/T0596 methods.

Embodiment 1-6 is used to illustrate polyurea compound for polyurea grease of two polyureas and preparation method thereof.

Embodiment 1

The preparation of graphene oxide：1g graphite flakes and 0.5g sodium nitrate are mixed with the 23ml concentrated sulfuric acids in ice bath It is even, 3g potassium permanganate is slowly added under stirring, temperature is maintained at 10 DEG C of 1h stirred below, and then mixture is in 35 DEG C of stirrings 0.5h, then adds the dilution of 50ml deionized waters, during release substantial amounts of heat, be less than 100 DEG C into exercising temperature in ice bath, 50ml water is added, mixture stirring 0.5h, adds 200ml deionized waters and further dilute.The 30 weight % of 10ml are added afterwards Aqueous hydrogen peroxide solution reduction potassium permanganate.Finally, mixture mass concentration is 5% hydrochloric acid（400ml）Washing and filtering, To remove metal ion.Then go to deacidify with 0.5L deionized waters, 60 DEG C of dry 24h, are made graphene oxide.

The preparation of graphene：0.1g graphene oxides obtained above are added to ultrasonic disperse in 100ml water（Ultrasonic wave Frequency is 30kHz）5ml hydrazine hydrates are added after 30min（Mass concentration is 85%）, 100 DEG C of reaction 24h of oil bath, what is finally obtained is black The powder that color flocculent deposit is obtained through washing, filter, after drying is graphene, and the performance of graphene is as shown in table 2 below.

The preparation of urea-base grease：

Material component：Graphene 2kg；500SN and the line miscella that subtracts three：64kg（100 DEG C of viscosity are 18mm²/s）；12 Amine 5.14kg；Para-totuidine 2.49kg；MDI6.03kg；The antioxidant T501 of 0.96kg；The T406 of 0.64kg

First 1kg graphenes, 5.14kg lauryl amines and 2.49kg para-totuidine are added in 22kg base oils, are heated to 80 DEG C, organic amine is melted completely；6.03kg MDI, 1kg graphenes are added into 21kg base oils again, heating makes its thawing；Will Above-mentioned two groups of solution mixing, is sufficiently stirred, reacts 10min, is continuously heating to 190 DEG C and carries out high temperature refining 20min；Add 21kg After base oil cools to 120 DEG C, the antioxidant T501 of 0.96kg is added；The T406 of 0.64kg, stirs evenly；Ground by three-roller 2-3 times is ground into fat.Properties of product are as shown in table 3.

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 For 35kHz）5ml hydrazine hydrates are added after 30min（Mass concentration is 85%）, 100 DEG C of reaction 24h of oil bath, the black wadding finally obtained It is graphene that shape, which precipitates the powder obtained through washing, filter, after drying, and the performance of graphene is as shown in table 2 below.

The preparation of two urea greases：

Material component：Graphene 2kg；500SN and the line miscella that subtracts three：62.4kg（100 DEG C of viscosity are 20mm²/s）；Ten Eight amine 8.51kg；Para-totuidine 3.26kg；TDI5.51kg；The antioxidant T501 of 0.96kg；The T406 of 0.64kg.

First 0.5kg graphenes, 8.51kg octadecylamines and 3.26kg para-totuidine are added in 20.4kg base oils, heated To 80 DEG C, organic amine is set to melt completely；5.51kg TDI, 1.5kg graphenes are added into 21kg base oils again, heating melts it Change；Above-mentioned two groups of solution is mixed, is sufficiently stirred, reaction 15min is continuously heating to 220 DEG C and carries out high temperature refining 5min；Add After 21kg base oils cool to 110 DEG C, the antioxidant T501 of 0.96kg is added；The T406 of 0.64kg, stirs evenly；Pass through three rollers Machine grinds 2-3 times into fat.Properties of product are as shown in table 3.

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 For 40kHz）5ml hydrazine hydrates are added after 30min（Mass concentration is 85%）, 100 DEG C of reaction 24h of oil bath, the black wadding finally obtained It is graphene that shape, which precipitates the powder obtained through washing, filter, after drying, and the performance of graphene is as shown in table 2 below.

The preparation of two urea greases：

Material component：Graphene 2kg；500SN and the line miscella that subtracts three：66.4kg（100 DEG C of viscosity are 23mm²/s）；Ten Diamines 4.52kg；Para-totuidine 2.19kg；TDI3.70kg；The antioxidant T501 of 0.96kg；The T406 of 0.64kg.

First 0.35kg graphenes, 4.52kg lauryl amines and 2.19kg para-totuidine are added in 24.4kg base oils, added Heat makes organic amine melt completely to 80 DEG C；3.70kgTDI, 1.65kg graphene are added into 21kg base oils again, heating makes it Melt；Above-mentioned two groups of solution is mixed, is sufficiently stirred, reaction 12min is continuously heating to 200 DEG C and carries out high temperature refining 10min；Add Enter after 21kg base oils cool to 100 DEG C, add the antioxidant T501 of 0.96kg；The T406 of 0.64kg, stirs evenly；Pass through three Roller machine grinds 2-3 times into fat.Properties of product are as shown in table 3.

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 For 25kHz）5ml hydrazine hydrates are added after 30min（Mass concentration is 85%）, 100 DEG C of reaction 24h of oil bath, the black wadding finally obtained It is graphene that shape, which precipitates the powder obtained through washing, filter, after drying, and the performance of graphene is as shown in table 2 below.

The preparation of two urea greases：

Material component：Graphene 2kg；500SN and the line miscella that subtracts three：63.2kg（100 DEG C of viscosity are 16mm²/s）；Ten Eight amine 5.10kg；Para-totuidine 1.95kg；MDI4.74kg；The antioxidant T501 of 0.96kg；The T406 of 0.64kg.

First 1.5kg graphenes, 5.10kg octadecylamines and 1.95kg para-totuidine are added in 21.2kg base oils, heated To 80 DEG C, organic amine is set to melt completely；4.74kg MDI, 0.5kg graphenes are added into 21kg base oils again, heating melts it Change；Above-mentioned two groups of solution is mixed, is sufficiently stirred, reaction 15min is continuously heating to 200 DEG C and carries out high temperature refining 12min；Add After 21kg base oils cool to 100 DEG C, the T406 of the antioxidant T501 and 0.64kg of 0.96kg are added；Stir evenly；Pass through three Roller machine grinds 2-3 times into fat.Properties of product are as shown in table 3.

Comparative example 1

Material component：In addition to not graphene-containing, remaining is the same as embodiment 4

Method according to embodiment 4 prepares polyurea grease, unlike, it is added without in the preparation process of two urea greases Graphene.Properties of product are as shown in table 3.

Comparative example 2

Raw material components are the same as embodiment 4

Method according to embodiment 4 prepares polyurea grease, unlike, whole graphenes add with antioxidant T501 Enter.The performance of polyurea grease product is as shown in table 3 below.

Comparative example 3

In addition to graphene is replaced by the crystalline flake graphite of phase homogenous quantities, remaining raw material components is the same as embodiment 4

Method according to embodiment 4 prepares polyurea grease, unlike, graphene by identical weight crystalline flake graphite generation Replace.The performance of polyurea grease product is as shown in table 3 below.

Embodiment 5

The preparation of graphene is the same as embodiment 1

Material component：With embodiment 4

A volume for 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add and lubricated with 5kg 5.10kg octadecylamines, the 1.95kg para-totuidine of base oil dissolving, are stirred 6 minutes, add what is dissolved with 5kg lubricating base oils 4.74kg MDI, are stirred 6 minutes, and 120 DEG C of constant temperature 20 minutes, obtains A systems.

The preparation of polyurea grease：Obtained A systems, 2kg graphenes are added in 42kg base oils and be sufficiently stirred, instead Answer 15min to be continuously heating to 200 DEG C and carry out high temperature refining 12min；After addition 21kg base oils cool to 100 DEG C, add The T406 of the antioxidant T501 and 0.64kg of 0.96kg；Stir evenly；2-3 times is ground into fat by three-roller.Properties of product are such as Shown in table 3.

Embodiment 6

Method according to embodiment 4 prepares polyurea grease, unlike, graphene use is commercially available from Beijing Ji'an letter section The model specification of trade Co., Ltd is the graphene product of G20（Purity>95%,

Graphene size 100-200nm）, gained grease product performance is as shown in table 3.

Table 2

Embodiment 7

The embodiment is used to illustrate polyurea compound for mixing polyurea grease and preparation method thereof.

The preparation of graphene is the same as embodiment 1

The preparation of polyurea grease：First by 1kg graphenes, 2.57kg lauryl amines, 4.03kg octadecylamines, 0.47kg ethylenediamines It is added to 1.24kg para-totuidine in 22kg base oils, is heated to 80 DEG C, organic amine is melted completely；Again to 21kg base oils MDI, 1kg graphene of middle addition 6.68kg, heating melt MDI；Above-mentioned two groups of solution is mixed, is sufficiently stirred, is reacted 10min, is continuously heating to 190 DEG C and carries out high temperature refining 20min；After addition 21kg base oils cool to 120 DEG C, 0.96kg is added Antioxidant T501；The T406 of 0.64kg, stirs evenly；2-3 times is ground into fat by three-roller.Properties of product are as shown in table 3.

Table 3

Embodiment 8-11 is used to illustrate polyurea compound for polyurea grease of four polyureas and preparation method thereof.

Embodiment 8

The preparation of graphene is the same as embodiment 1

The preparation of four urea greases：

Material component：Graphene 15g；The 500SN and line miscella 620g that subtracts three（100 DEG C of viscosity are 15mm²/s）；Octadecylamine 80.59g；Ethylenediamine 9.41g；MDI73.26g；8g antioxidant T501；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 200 grams of base oils and 73.26 grams of MDI Hybrid Heatings to 60 DEG C, 9.41 grams of ethylenediamines are added, 80 DEG C are warming up to, reacts 30min；Again by 7 grams of graphenes, 210 grams of base oils and 80.59 grams of octadecylamine Hybrid Heatings to 60 DEG C； By above two solution Hybrid Heating, 30min is reacted；210 DEG C are warming up to, keeps 10min, adds 210 grams of base oils thereto It is cooled to 110 DEG C of additions, 8 grams of antioxidant T501；12 grams of dialkyl dithiocarbamates, stir evenly, are ground by three-roller 2-3 times is ground into fat.Properties of product are as shown in table 4.

Embodiment 9

The preparation of graphene is the same as embodiment 1.

The preparation of four urea greases：

Material component：Graphene 15g；The 500SN and line miscella 676g that subtracts three（100 DEG C of viscosity are 17mm²/s）；Octadecylamine 60.03g；Ethylenediamine 7.29g；TDI39.12g；8g antioxidant T501；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 256 grams of base oils and 39.12 grams of TDI Hybrid Heatings to 60 DEG C, 7.29 grams of ethylenediamines are added, 80 DEG C are warming up to, reacts 30min；Again by 7 grams of graphenes, 210 grams of base oils and 60.03 grams of octadecylamine Hybrid Heatings to 60 DEG C； By above two solution Hybrid Heating, 30min is reacted；210 DEG C are warming up to, keeps 10min, adds 210 grams of base oils thereto It is cooled to 110 DEG C of additions, 8 grams of antioxidant T501；12 grams of dialkyl dithiocarbamates, stir evenly, are ground by three-roller 2-3 times is ground into fat.Properties of product are as shown in table 4.

Embodiment 10

The preparation of graphene is the same as embodiment 1.

The preparation of four urea greases：

Material component：Graphene 15g；The 500SN and line miscella 636g that subtracts three（100 DEG C of viscosity are 21mm²/s）；Lauryl amine 75.01g；Ethylenediamine 11.07g；TDI61.23g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 216 grams of base oils and 61.23 grams of TDI Hybrid Heatings to 60 DEG C, 11.07 grams of second two are added Amine, is warming up to 80 DEG C, reacts 30min；Again by 7 grams of graphenes, 210 grams of base oils and 75.01 grams of lauryl amine Hybrid Heatings to 60 ℃；By above two solution Hybrid Heating, 30min is reacted；210 DEG C are warming up to, keeps 10min, adds 210 grams of bases thereto Oil is cooled to 110 DEG C of additions, 8 grams of antioxidant T501；12 grams of dialkyl dithiocarbamates, stir evenly, pass through three-roller 2-3 times is ground into fat.Properties of product are as shown in table 4.

Embodiment 11

The preparation of graphene is the same as embodiment 1.

The preparation of four urea greases：

Material component：Graphene 15g；The 500SN and line miscella 644g that subtracts three（100 DEG C of viscosity are 23mm²/s）；Lauryl amine 59.73g；Ethylenediamine 9.37g；MDI69.98g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 224 grams of base oils and 69.98 grams of MDI Hybrid Heatings to 60 DEG C, 9.37 grams of ethylenediamines are added, 80 DEG C are warming up to, reacts 30min；Again by 7 grams of graphenes, 210 grams of base oils and 59.73 grams of lauryl amine Hybrid Heatings to 60 DEG C； By above two solution Hybrid Heating, 30min is reacted；210 DEG C are warming up to, keeps 10min, adds 210 grams of base oils thereto It is cooled to 110 DEG C of additions, 8 grams of antioxidant T501；12 grams of dialkyl dithiocarbamates, stir evenly, are ground by three-roller 2-3 times is ground into fat.Properties of product are as shown in table 4.

Comparative example 4

Material component：The 500SN and line miscella 660g that subtracts three（100 DEG C of viscosity are 19mm²/s）；Octadecylamine 59.76g；Second Diamines 7.01g；MDI55.81g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 240 grams of base oils and 55.81 grams of MDI Hybrid Heatings to 60 DEG C, 7.01 grams of ethylenediamines are added, are warming up to 80 DEG C, react 30min；Again by 210 grams of base oils and 59.76 grams of octadecylamine Hybrid Heatings to 60 DEG C；Above two solution is mixed Heating, reacts 30min；210 DEG C are warming up to, keeps 10min, 210 grams of base oils is added thereto and is cooled to 110 DEG C of 8 grams of additions Antioxidant T501；12 grams of dialkyl dithiocarbamates, stir evenly, and 2-3 times is ground into fat by three-roller.Product Can be as shown in table 4.

Table 4

	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Comparative example 4
						Fatty amine	Octadecylamine	Octadecylamine	Lauryl amine	Lauryl amine	Octadecylamine
Diamines	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine
						Isocyanates	MDI	TDI	TDI	MDI	MDI
Dropping point, DEG C	>300	>300	>300	>300	>300
						Work cone penetration, 0.1mm	230	239	237	237	245
Initial temperature is aoxidized, DEG C	262	256	260	258	232
						Stencil oil-dividing (100 DEG C, 30h) %	0.2	0.3	0.5	0.3	0.6
Anticorrosive property（52 DEG C, 48h）	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified
						Water drenches number of dropouts（38 DEG C, 1h）, %	0.5	0.8	0.6	0.6	1.4
Tetra-ball machine test, PB, kgf	70	60	60	60	60
						Tetra-ball machine test, PD, kgf	500	500	500	500	400
Copper corrosion	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified

Embodiment 12-15 is used to illustrate polyurea compound for polyurea grease of six polyureas and preparation method thereof.

Embodiment 12

The preparation of graphene is the same as embodiment 1

The preparation of Hexaurea lubricating grease：

Material component：Graphene 15g；The miscella 660g of 500SN and the line that subtracts three（100 DEG C of viscosity are 19mm²/s）；18 Amine 55g；Ethylenediamine 12.86g；TDI54.23g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

The mixture of 8 grams of graphenes, 36.23 grams of TDI and 180 gram of base oils is heated to 60 DEG C, then by 7 grams of graphenes, 180 grams of base oils and 55 grams of octadecylamine Hybrid Heatings to 60 DEG C and are slowly added into above-mentioned system, are warming up to 80 DEG C instead Answer 30 minutes, be slowly added to 12.86 grams of ethylenediamines, isothermal reaction 30min, 18 grams of TDI and 150 gram of base oils are finally mixed add Heat is added in system to 50 DEG C, and 80 DEG C of constant temperature reacts 30 minutes, is warming up to 120 DEG C and is kept for 30 minutes, then heats to 210 DEG C, kept for 10 minutes, add 150 grams of base oil cooling downs, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501；12 Gram dialkyl dithiocarbamate, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 5.

Embodiment 13

The preparation of graphene is the same as embodiment 1.

The preparation of Hexaurea lubricating grease：

Material component：Graphene 15g；The miscella 620g of 500SN and the line that subtracts three（100 DEG C of viscosity are 17mm²/s）；18 Amine 62.13g；Ethylenediamine 14.57g；MDI86.23g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

The mixture of 8 grams of graphenes, 58.23 grams of MDI and 160 gram of base oils is heated to 60 DEG C, then by 7 grams of graphenes, 160 grams of base oils and 62.13 grams of octadecylamine Hybrid Heatings to 60 DEG C and are slowly added into above-mentioned system, are warming up to 80 DEG C Reaction 30 minutes, is slowly added to 14.57 grams of ethylenediamines, isothermal reaction 30min, finally mixes 28 grams of MDI and 150 gram of base oils 50 DEG C are heated to, is added in system, 80 DEG C of constant temperature reacts 30 minutes, is warming up to 120 DEG C and is kept for 30 minutes, is then heated to 210 DEG C, kept for 10 minutes, add 150 grams of base oil cooling downs, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501； 12 grams of dialkyl dithiocarbamates, stir evenly, and 2-3 times is ground into fat by three-roller.The properties of product such as institute of table 5 Show.

Embodiment 14

The preparation of graphene is the same as embodiment 1.

The preparation of Hexaurea lubricating grease：

Material component：Graphene 15g；The miscella 676g of 500SN and the line that subtracts three（100 DEG C of viscosity are 21mm²/s）；12 Amine 42.07g；Ethylenediamine 12.19g；TDI51.92g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

The mixture of 8 grams of graphenes, 34.92 grams of TDI and 188 gram of base oils is heated to 60 DEG C, then by 7 grams of graphenes, 188 grams of base oils and 42.07 grams of lauryl amine Hybrid Heatings to 60 DEG C and are slowly added into above-mentioned system, are warming up to 80 DEG C Reaction 30 minutes, is slowly added to 12.19 grams of ethylenediamines, isothermal reaction 30min, finally mixes 17 grams of TDI and 150 gram of base oils 50 DEG C are heated to, is added in system, 80 DEG C of constant temperature reacts 30 minutes, is warming up to 120 DEG C and is kept for 30 minutes, is then heated to 210 DEG C, kept for 10 minutes, add 150 grams of base oil cooling downs, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501； 12 grams of dialkyl dithiocarbamates, stir evenly, and 2-3 times is ground into fat by three-roller.The properties of product such as institute of table 5 Show.

Embodiment 15

The preparation of graphene is the same as embodiment 1.

The preparation of Hexaurea lubricating grease：

Material component：Graphene 15g；The miscella 636g of 500SN and the line that subtracts three（100 DEG C of viscosity are 22mm²/s）；12 Amine 48.33g；Ethylenediamine 14.18g；MDI84.33g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

The mixture of 8 grams of graphenes, 56.33 grams of MDI and 168 gram of base oils is heated to 60 DEG C, then by 7 grams of graphenes, 168 grams of base oils and 48.33 grams of lauryl amine Hybrid Heatings to 60 DEG C and are slowly added into above-mentioned system, are warming up to 80 DEG C Reaction 30 minutes, is slowly added to 14.18 grams of ethylenediamines, isothermal reaction 30min, finally mixes 28 grams of MDI and 150 gram of base oils 50 DEG C are heated to, is added in system, 80 DEG C of constant temperature reacts 30 minutes, is warming up to 120 DEG C and is kept for 30 minutes, is then heated to 210 DEG C, kept for 10 minutes, add 150 grams of base oil cooling downs, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501； 12 grams of dialkyl dithiocarbamates, stir evenly, and 2-3 times is ground into fat by three-roller.The properties of product such as institute of table 5 Show.

Comparative example 5

Material component：The miscella 640g of 500SN and the line that subtracts three（100 DEG C of viscosity are 19mm²/s）；Octadecylamine 53g；Second two Amine 12.51g；MDI73.5g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

The mixture of 49.5 grams of MDI and 170 gram of base oils is heated to 60 DEG C, then by 170 grams of base oils and 55 gram 18 Amine Hybrid Heating is to 60 DEG C and is slowly added into above-mentioned system, is warming up to 80 DEG C and reacts 30 minutes, is slowly added to 12.51 Gram ethylenediamine, 24 grams of MDI and 150 gram of base oil Hybrid Heatings, are finally added in system by isothermal reaction 30min to 50 DEG C, 80 DEG C of constant temperature reacts 30 minutes, is warming up to 120 DEG C and is kept for 30 minutes, then heat to 210 DEG C, kept for 10 minutes, adds 150 grams Base oil cooling down, treats that temperature is cooled to 110 DEG C, adds 8 grams of antioxidant T501；12 grams of dialkyldithiocarbamacompositions Salt, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 5.

Table 5

	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Comparative example 5
						Fatty amine	Octadecylamine	Octadecylamine	Lauryl amine	Lauryl amine	Octadecylamine
Diamines	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine
						Isocyanates	TDI	MDI	TDI	MDI	MDI
Dropping point, DEG C	>310	>310	>310	>310	>310
						Work cone penetration, 0.1mm	235	232	236	234	242
Initial temperature is aoxidized, DEG C	261	265	263	259	231
						100 DEG C of Stencil oil-dividing, 30h, %	0.6	0.5	0.6	0.5	0.8
Anticorrosive property（52 DEG C, 48h）	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified
						Water drenches number of dropouts（38 DEG C, 1h）, %	0.8	0.6	0.8	0.7	1.2
Tetra-ball machine test, PB, kgf	60	60	60	60	50
						Tetra-ball machine test, PD, kgf	500	500	500	500	315
Copper corrosion	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified

Embodiment 16-19 is used to illustrate polyurea compound for polyurea grease of eight polyureas and preparation method thereof.

Embodiment 16

The preparation of graphene is the same as embodiment 1

The preparation of eight urea greases：

Raw material components：Graphene 15g；The 500SN and line miscella 676g that subtracts three（100 DEG C of viscosity 11mm²/s）；Octadecylamine 40g；Ethylenediamine 14.5g；TDI52.5g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 233 grams of base oils and 52.5 grams of TDI Hybrid Heatings to 50 DEG C, 9.7 grams of ethylenediamines are added, are risen Temperature is to 80 DEG C, after reacting 30 minutes, adds 4.8 grams of ethylenediamines, reacts 30 minutes, by 7 grams of graphenes, 233 grams of base oils It is added to 40 grams of octadecylamine Hybrid Heatings to 60 DEG C in said mixture, is warming up to 80 DEG C, is reacted 30 minutes, be continuously heating to 210 DEG C, kept for 10 minutes, add 210 grams of base oils, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501；12 gram two Diethyldithiocarbamate, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 6.

Embodiment 17

The preparation of graphene is the same as embodiment 1

The preparation of eight urea greases：

Raw material components：Graphene 15g；The 500SN and line miscella 620g that subtracts three（100 DEG C of viscosity 11mm²/s）；Octadecylamine 51.5g；Ethylenediamine 17.3g；MDI95g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 205 grams of base oils and 95 grams of MDI Hybrid Heatings to 50 DEG C, 11.3 grams of ethylenediamines are added, are risen Temperature after reaction 30 minutes, adds 6 grams of ethylenediamines, reacts 30 minutes to 80 DEG C, by 7 grams of graphenes, 205 grams of base oils with 51.5 grams of octadecylamine Hybrid Heatings are added in said mixture to 60 DEG C, are warming up to 80 DEG C, are reacted 30 minutes, are continuously heating to 210 DEG C, kept for 10 minutes, add 210 grams of base oils, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501；12 gram two Diethyldithiocarbamate, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 6.

Embodiment 18

The preparation of graphene is the same as embodiment 1

The preparation of eight urea greases：

Raw material components：Graphene 15g；The 500SN and line miscella 636g that subtracts three（100 DEG C of viscosity 11mm²/s）；Lauryl amine 48g；Ethylenediamine 20.5g；TDI78g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 213 grams of base oils and 78 grams of TDI Hybrid Heatings to 50 DEG C, 13.5 grams of ethylenediamines are added, are risen Temperature after reaction 30 minutes, adds 7 grams of ethylenediamines, reacts 30 minutes to 80 DEG C, by 7 grams of graphenes, 213 grams of base oils with 48 grams of lauryl amine Hybrid Heatings are added in said mixture to 60 DEG C, are warming up to 80 DEG C, are reacted 30 minutes, are continuously heating to 210 DEG C, kept for 10 minutes, add 210 grams of base oils, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501；12 gram two Diethyldithiocarbamate, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 6.

Embodiment 19

The preparation of graphene is the same as embodiment 1

The preparation of eight urea greases：

Raw material components：Graphene 15g；The 500SN and line miscella 660g that subtracts three（100 DEG C of viscosity 11mm²/s）；Lauryl amine 32.4g；Ethylenediamine 14.7g；MDI75.5g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 8 grams of graphenes, 225 grams of base oils and 75.5 grams of MDI Hybrid Heatings to 50 DEG C, 9.7 grams of ethylenediamines are added, are risen Temperature after reaction 30 minutes, adds 5 grams of ethylenediamines, reacts 30 minutes to 80 DEG C, by 7 grams of graphenes, 225 grams of base oils with 32.4 grams of lauryl amine Hybrid Heatings are added in said mixture to 60 DEG C, are warming up to 80 DEG C, are reacted 30 minutes, are continuously heating to 210 DEG C, kept for 10 minutes, add 210 grams of base oils, treated that temperature is cooled to 110 DEG C, add 8 grams of antioxidant T501；12 gram two Diethyldithiocarbamate, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 6.

Comparative example 6

Raw material components：The 500SN and line miscella 644g that subtracts three（100 DEG C of viscosity 11mm²/s）；Octadecylamine 52.8g；Ethylenediamine 18.6g；TDI68.2g；Antioxidant T5018g；Dialkyl dithiocarbamate 12g.

First by 217 grams of base oils and 68.2 grams of TDI Hybrid Heatings to 50 DEG C, 12.6 grams of ethylenediamines are added, are warming up to 80 DEG C, After reaction 30 minutes, 6 grams of ethylenediamines are added, are reacted 30 minutes, by 217 grams of base oils and 52.8 grams of octadecylamine Hybrid Heatings It is added to 60 DEG C in said mixture, is warming up to 80 DEG C, reacted 30 minutes, be continuously heating to 210 DEG C, is kept for 10 minutes, then 210 grams of base oils are added, treats that temperature is cooled to 110 DEG C, adds 8 grams of antioxidant T501；12 grams of dialkyldithiocarbamacompositions Salt, stirs evenly, and 2-3 times is ground into fat by three-roller.Properties of product are as shown in table 6.

Table 6

	Embodiment 16	Embodiment 17	Embodiment 18	Embodiment 19	Comparative example 6
						Fatty amine	Octadecylamine	Octadecylamine	Lauryl amine	Lauryl amine	Octadecylamine
Diamines	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine	Ethylenediamine
						Isocyanates	TDI	MDI	TDI	MDI	TDI
Dropping point, DEG C	>330	>330	>330	>330	315
						Work cone penetration, 0.1mm	246	242	243	245	269
Initial temperature is aoxidized, DEG C	270	271	2768	266	238
						Stencil oil-dividing (100 DEG C, 30h), %	0.6	0.5	0.5	0.6	0.6
Anticorrosive property（52 DEG C, 48h）	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified
						Water drenches number of dropouts（38 DEG C, 1h）,%	0.5	0.3	0.4	0.5	1.0
Tetra-ball machine test, PB, kgf	70	70	70	70	60
						Tetra-ball machine test, PD, kgf	500	500	500	500	400
Copper corrosion	It is qualified	It is qualified	It is qualified	It is qualified	It is qualified

Can be seen that polyurea grease of the invention from the result of above-mentioned table 3 to table 6 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, during present invention is not limited to the embodiments described above 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

A kind of 1. polyurea grease, it is characterised in that on the basis of the polyurea grease weight, including following components：0.2-15 The graphene of weight %；The polyurea compound of 4-30 weight %；The base oil of 65-95 weight %, the preparation of the polyurea grease Method includes：

(1) part graphene, organic amine and part basis oil Hybrid Heating, heating are treated that organic amine melts completely；

(2) diisocyanate, remainder graphene and part basis oil Hybrid Heating are made into its thawing；

(3) mixed solution obtained by step (1) and step (2) is mixed and reacted, be then warming up to 180-230 DEG C of constant temperature refining System, cooling, adds surplus base oil, adds necessary additive, obtain finished product.
2. polyurea grease according to claim 1, wherein, on the basis of the polyurea grease weight, including with the following group Point：The graphene of 1-10 weight %；The polyurea compound of 6-25 weight %；The base oil of 70-93 weight %.
3. polyurea grease according to claim 1 or 2, wherein, the graphene can disperse in 1ml base oils and Non-setting amount is 8-12mg.
4. polyurea grease according to claim 1 or 2, wherein, the particle diameter of the graphene is 80-800nm, electrical conductivity For 700-900S/cm, decomposition temperature is 430-480 DEG C.
5. polyurea grease according to claim 1 or 2, wherein, the polyurea compound is two polyurea compounds, four gather At least one of carbamide compound, six polyurea compounds and eight polyurea compounds.
6. polyurea grease according to claim 5, wherein, the polyurea compound is two polyurea compounds, the chemical combination Thing has with lower structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R³It is arlydene, alkylidene or cycloalkylidene.
7. polyurea grease according to claim 6, wherein, R¹It is phenyl or substituted phenyl, or the alkane that carbon number is 8-24 Base or cycloalkyl；R³It is the arlydene, alkylidene or cycloalkylidene of 6-30.
8. polyurea grease according to claim 7, wherein, R¹It is the alkyl of phenyl or C1-C3 or the benzene of halogen substitution Base, or the alkyl or cycloalkyl that carbon number is 10-20, R³It is With-(CH₂)₆- At least one of.
9. polyurea grease according to claim 5, wherein, the polyurea compound is four polyurea compounds, the chemical combination Thing has with lower structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.
10. polyurea grease according to claim 5, wherein, six polyurea compound has with lower structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.
11. polyurea grease according to claim 5, wherein, the polyurea compound is eight polyurea compounds, the chemical combination Thing has with lower structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.
12. according to the polyurea grease described in any one in claim 9-11, wherein, R¹It is phenyl or substituted phenyl, or Carbon number is the alkyl or cycloalkyl of 8-24；R²It is the alkylidene of phenylene or biphenylene or carbon number for 2-12；R³It is that carbon number is 6- 30 arlydene, alkylidene or cycloalkylidene.
13. polyurea grease according to claim 12, wherein, R¹It is phenyl or C1-C3 alkyl or the benzene of halogen substitution Base, or the alkyl or cycloalkyl that carbon number is 10-18, R²It is phenylene or biphenylene, or carbon number is the alkylidene of 2-8；R³It is selected from With-(CH₂)₆- at least It is a kind of.
14. the polyurea grease according to any one in claim 1 or 2, wherein, which also contains 0.5- The additive of 15 weight %.
15. the polyurea grease according to any one in claim 1 or 2, wherein, the organic amine is monoamine, and two is different The molar ratio of cyanate and monoamine is 1:2.
16. a kind of preparation method of polyurea grease, it is characterised in that this method includes：

(1) part graphene, organic amine and part basis oil Hybrid Heating, heating are treated that organic amine melts completely；

(2) diisocyanate, remainder graphene and part basis oil Hybrid Heating are made into its thawing；

(3) mixed solution obtained by step (1) and step (2) is mixed and reacted, be then warming up to 180-230 DEG C of constant temperature refining System, cooling, adds surplus base oil, adds necessary additive, obtain finished product；

The dosage of graphene, diisocyanate and base oil causes on the basis of obtained polyurea grease weight, graphene Content is 0.2-15 weight %, and the content of polyurea compound is 4-30 weight %, and the content of base oil is 65-95 weight %.
17. preparation method according to claim 16, wherein, the organic amine is monoamine, diisocyanate and monoamine Molar ratio is 1:2.
18. the preparation method according to claim 16 or 17, wherein, the graphene can disperse in 1ml base oils And non-setting amount is 8-12mg.
19. the preparation method according to claim 16 or 17, wherein, the particle diameter of the graphene is 80-800nm, conductance Rate is 700-900S/cm, and decomposition temperature is 430-480 DEG C.
20. the preparation method according to claim 16 or 17, wherein, the dosage of graphene, diisocyanate and base oil So that on the basis of obtained polyurea grease weight, the content of graphene is 1-10 weight %；The content of polyurea compound is 6-25 weight %；The content of base oil is 70-93 weight %.
21. preparation method according to claim 17, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is Carbon number is arlydene, alkylidene or the cycloalkylidene of 6-30；

The structural formula of the monoamine is R¹-NH₂, wherein, R¹It is phenyl or C1-C3 alkyl or the phenyl of halogen substitution, or carbon number is The alkyl or cycloalkyl of 10-20.
22. preparation method according to claim 21, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), first Base diphenyl diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and an xyxylene two At least one of isocyanates；

The monoamine is fatty amine and the mixture of arylamine, and the molar ratio of the two is 0.5-2:1.
23. preparation method according to claim 22, wherein, the arylamine is selected from aniline, m-chloroaniline, parachloroanilinum And/or the arylamine of para-totuidine, the fatty amine are the fatty amines selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
24. a kind of preparation method of polyurea grease, it is characterised in that this method includes：

(1) by part graphene, diisocyanate and part basis oil Hybrid Heating to 50-60 DEG C, diamines is added, is warming up to 80-100 DEG C, react 20-60 minutes；

(2) by monoamine, remainder graphene and part basis oil Hybrid Heating to 50-60 DEG C；

(3) mixed solution obtained by step (1) and step (2) is mixed and reacted, be then warming up to 180-230 DEG C of constant temperature refining System, cooling, adds surplus base oil, adds necessary additive, obtain finished product；

The dosage of graphene, diisocyanate and base oil causes on the basis of obtained polyurea grease weight, graphene Content is 0.2-15 weight %, and the content of polyurea compound is 4-30 weight %, and the content of base oil is 65-95 weight %.
25. preparation method according to claim 24, wherein, the molar ratio of diisocyanate, diamines and monoamine is 2:1: 2。
26. a kind of preparation method of polyurea grease, it is characterised in that this method includes：

(1) by part graphene, diisocyanate and part basis oil Hybrid Heating to 50-70 DEG C；

(2) by monoamine, remainder graphene and part basis oil Hybrid Heating to 50-70 DEG C；

(3) mixed solution obtained by step (1) and step (2) is mixed and heated up and reacted, then add diamines, react 20- 60 minutes；

(4) it is added to after the oily and remaining diisocyanate of part basis being heated to 50-70 DEG C in step (3) products therefrom, Reacted 20-60 minutes at 80-100 DEG C, continue to be warming up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add Enter necessary additive, obtain finished product；

The dosage of graphene, diisocyanate and base oil causes on the basis of obtained polyurea grease weight, graphene Content is 0.2-15 weight %, and the content of polyurea compound is 4-30 weight %, and the content of base oil is 65-95 weight %.
27. preparation method according to claim 26, wherein, each added diisocyanate, monoamine, diamines and two The molar ratio of isocyanates is 2:2:2:1.
28. a kind of preparation method of polyurea grease, it is characterised in that this method includes：

(1) by part graphene, diisocyanate and part basis oil Hybrid Heating to 50-70 DEG C, add diamines and be warming up to 80- 90 DEG C are reacted 20-60 minutes, are slowly added to diamines again, are reacted 20-60 minutes at 80-90 DEG C；

(2) by monoamine, remainder graphene and part basis oil Hybrid Heating to 50-70 DEG C；

(3) mixed solution obtained by step (1) and step (2) is mixed and is warming up at 80-90 DEG C and reacted 20-60 minutes, continued 180-220 DEG C of constant temperature refining is warming up to, cooling, adds surplus base oil, add necessary additive, obtain finished product；

The dosage of graphene, diisocyanate and base oil causes on the basis of obtained polyurea grease weight, graphene Content is 0.2-15 weight %, and the content of polyurea compound is 4-30 weight %, and the content of base oil is 65-95 weight %.
29. preparation method according to claim 28, wherein, each added diisocyanate, diamines, diamines and monoamine Molar ratio be 4:2:1:2.
30. according to the preparation method described in any one in claim 24-29, wherein, the structural formula of the diamines is NH₂- R²-NH₂, wherein, R²It is the alkylidene that carbon number is 2-8, or phenylene or biphenylene.
31. preparation method according to claim 30, wherein, the diamines is selected from p-phenylenediamine, o-phenylenediamine, 4,4- The aromatic amine of benzidine and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.
32. according to the preparation method described in any one in claim 24-29, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is arlydene, alkylidene or the cycloalkylidene that carbon number is 6-30；

The structural formula of the monoamine is R¹-NH₂, wherein, R¹It is phenyl or C1-C3 alkyl or the phenyl of halogen substitution, or carbon number is The alkyl or cycloalkyl of 10-20.
33. preparation method according to claim 32, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), first Base diphenyl diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and an xyxylene two At least one of isocyanates；

The monoamine is fatty amine and the mixture of arylamine, and the molar ratio of the two is 0.5-2:1.
34. preparation method according to claim 33, wherein, the arylamine is selected from aniline, m-chloroaniline, parachloroanilinum And/or the arylamine of para-totuidine, the fatty amine are the fatty amines selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
35. according to the preparation method described in any one in claim 24-29, wherein,

The dosage of graphene, diisocyanate and base oil causes on the basis of obtained polyurea grease weight, graphene Content is 1-10 weight %；The content of polyurea compound is 6-25 weight %；The content of base oil is 70-93 weight %.
36. according to the preparation method described in any one in claim 24-29, wherein, the graphene is in 1ml base oils Can scattered and non-setting amount be 8-12mg.
37. according to the preparation method described in any one in claim 24-29, wherein, the particle diameter of the graphene is 80- 800nm, electrical conductivity 700-900S/cm, decomposition temperature are 430-480 DEG C.
38. the polyurea grease as made from the preparation method described in any one in claim 21-37.