CN104560265A - Polyurea lubricating grease and preparation method thereof - Google Patents
Polyurea lubricating grease and preparation method thereof Download PDFInfo
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- CN104560265A CN104560265A CN201310516334.XA CN201310516334A CN104560265A CN 104560265 A CN104560265 A CN 104560265A CN 201310516334 A CN201310516334 A CN 201310516334A CN 104560265 A CN104560265 A CN 104560265A
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Abstract
The invention discloses polyurea lubricating grease, which is characterized in that based on the weight of the lubricating grease, the lubricating grease comprises the following components: 0.2-15% of grapheme, 4-30% of a polyurea compound, 65-95% of base oil and 0.5-15% of an additive. The invention also discloses a preparation method of the polyurea lubricating grease and the prepared polyurea lubricating grease. The polyurea lubricating grease disclosed by the invention not only has excellent corrosion resistance and salt fog resistance, but also has the properties such as excellent heat temperature resistance, water resistance, adhesivity, colloid stability and extreme pressure antiwear property, and has a long service life. The polyurea lubricating grease disclosed by the invention is simple in preparation process, environmental friendly, low in cost and stable in product quality.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of polyurea grease and preparation method thereof.
Background technology
Urea-base grease is obtained by organic compound urea multiviscosisty mineral oil or synthetic oil, viscosifying agent is metal ion not, avoid the katalysis that metal ion is oxidized base oil, urea-base grease has good oxidation stability, heat-resistant quality and other various premium propertiess, also there is work-ing life long especially, it is a kind of multipurpose grease, various lubricating grease can be prepared and meet different service requirementss, be used in high temperature, low temperature, high loading, wide velocity range and the occasion contacted with impedance dielectric, be widely used in electrical equipment, metallurgical, food, automobile, the industries such as papermaking.
There is a large amount of patent to inquire into the performance of two urea greases in recent years, prepare polyurea grease as US5158694 is reacted by vulcabond and water and amine, but the dropping point of its product is between 230-260 DEG C; CN1272530A, under the existence of base oil, makes C8-C24 aliphatic amide and excessive di-isocyanate reaction, is neutralized by unreacted vulcabond with water, and continuing reaction to temperature is 130-200 DEG C, and the standby two urea grease dropping points of this legal system reach 260-330 DEG C; Organic amine and isocyanic ester mix and react by CN1580211A, after temperature of charge is elevated to 100-150 DEG C, adds quenching oil and material is cooled rapidly, grind to form fat, and the standby urea-base grease of this legal system has stable vibration values; Base oil, alkylamine and excessive vulcabond mix at 50-120 DEG C by CN1408825A, react, and add in excessive water and unreacted vulcabond, are warming up to melting, add quenching oil, cool out the lubricating grease that still obtains appearance transparent; CN101368129A has added boratory extreme pressure anti-wear additives in system, improves the over-all properties of lubricating grease, reduces cost; CN1657599A improves the oxidation stability of lubricating grease by adding calcium containing compound in polyurea grease, its complex process.CN101111591A refer to four urea greases, but preparation technology's more complicated, but also introduce metal ion, this will affect the oxidation stability of polyurea grease; CN101693851A adopt two ureas, triuret, four ureas mixture and introduce the fat that amide salt viscosifying agent obtains there is excellent high-temperature behavior, resistance leachability, good extreme pressure anti-wear; CN1056313A viscosifying agent used is two ureas and four urea mixtures, and this fat has more excellent performance in the machinery of long-term operation.
In recent years in order to improve the performance of two urea greases, four urea greases, six urea greases and eight urea greases, in additive, have also been made large quantifier elimination, such as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc.Nano material gradually in the application of lubricating grease, as nano silicon, Nano diamond, nano titanium oxide, nano zine oxide etc., but does not still have the correlative study of the application of Graphene in lubricating grease so far yet.
Summary of the invention
The object of this invention is to provide polyurea grease of a kind of graphene-containing and preparation method thereof.
The present inventor finds under study for action, Graphene is joined in base oil as the part of viscosifying agent in initial reaction stage, react with polyurea thickening agent one and generate the polyurea grease of graphene-containing, the polyurea grease obtained not only has good conductivity, and the method obviously can shorten the preparation time of polyurea grease.
Therefore, on the one hand, the invention provides a kind of polyurea grease, it is characterized in that, with lubricating grease weight for benchmark, comprise following component: the Graphene of 0.2-15 % by weight; The polyurea compound of 4-30 % by weight; The base oil of 65-95 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the Graphene of 1-10 % by weight; The polyurea compound of 6-25 % by weight; The base oil of 70-93 % by weight.
Second aspect, the invention provides the preparation method of polyurea grease as above, it is characterized in that, the method comprises: Graphene, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of polyurea grease, it is characterized in that, the method comprises:
(1) by part Graphene, organic amine and part basis oil Hybrid Heating, heat up and treat that organic amine melts completely;
(2) it is made to melt vulcabond, remainder Graphene and part basis oil Hybrid Heating;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Fourth aspect, the invention provides a kind of preparation method of polyurea grease, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-60 DEG C, add diamines, be warmed up to 80-100 DEG C, react 10-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-60 DEG C;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
5th aspect, the invention provides a kind of preparation method of polyurea grease, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond 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) step (1) and step (2) gained mixing solutions are mixed and heat up react, then add diamines, reaction 10-60 minute;
(4) join in step (3) products therefrom after part basis oil and remaining vulcabond being heated to 50-70 DEG C, at 80-100 DEG C, react 10-60 minute, continue to be warmed up to 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
6th aspect, the invention provides a kind of preparation method of polyurea grease, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-70 DEG C, add diamines be warming up to 80-90 DEG C react 20-60 minute, again slowly add diamines, at 80-90 DEG C, react 10-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-70 DEG C;
(3) step (1) and step (2) gained mixing solutions mixed and react 10-60 minute at being warming up to 80-90 DEG C, continue to be warmed up to 180-220 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
7th aspect, the invention provides the polyurea grease obtained by method as above.
The polyurea grease of the present invention's synthesis has the advantage of general urea-base grease, as good colloid stability, high temperatures, low temperature properties, extreme pressure anti-wear etc., more improves its resistance of oxidation adding of Graphene simultaneously.And add due to the preliminary stage of Graphene at fat processed, make greatly to improve into fat speed, shorten saponification time, but also make the polyurea grease obtained can be competent in high temperature, at a high speed, the harsh working condition such as high loading, many water.Trace it to its cause, may be make viscosifying agent depend on the structure forming class micelle around it because of the Graphene added at fat preliminary stage processed as nucleus, this synergy between Graphene and soap molecule enhances the ability of the molecules immobilized base oil of soap.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of polyurea grease, with this polyurea grease weight for benchmark, comprise following component: the Graphene of 0.2-15 % by weight; The polyurea compound of 4-30 % by weight; The base oil of 65-95 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the Graphene of 1-10 % by weight; The polyurea compound of 6-25 % by weight; The base oil of 70-93 % by weight.
In polyurea grease of the present invention, the large usage quantity of Graphene, with polyureas jointly as viscosifying agent, and unconventional conductive agent, gained polyurea grease is made to maintain the advantage of general urea-base grease on the one hand, as good colloid stability, high temperatures, low temperature properties, extreme pressure anti-wear etc., more improve its resistance of oxidation adding of Graphene simultaneously.On the other hand because the preliminary stage of Graphene at fat processed adds, make greatly to improve into fat speed, shorten saponification time, but also make the polyurea grease obtained can be competent in high temperature, at a high speed, the harsh working condition such as high loading, many water.
Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, be at present in the world the thinnest be the hardest nano material also, its thermal conductivity is up to 5300W/mK, higher than carbon nanotube and diamond, and its resistivity than copper or silver lower, be the material that at present resistivity is minimum in the world.Because Graphene is in fact a kind of transparent, good conductor, also be applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell, it is widely used in the fields such as nanoelectronics, nano-complex, battery, ultracapacitor, hydrogen storage and biologic applications.
In the present invention, described Graphene can be the Graphene of existing all size, by commercially available, also can be obtained by existing various method.Under preferable case, described Graphene is obtained by the method comprised the following steps:
Graphite flakes and SODIUMNITRATE, the vitriol oil are mixed in ice bath, under stirring, slowly adds potassium permanganate, stirring reaction at 10 DEG C, be warming up to 35 DEG C and continue stirring reaction, then add deionized water dilution.In system, add superoxol reduction potassium permanganate, then obtain graphene oxide through pickling, washing, drying.After obtained graphene oxide is added to the water ultrasonic wave, add hydrazine hydrate, after oil bath sufficient reacting, the black flocks obtained is through washing, suction filtration, drying, and the powder finally obtained is Graphene.
The Graphene (being called self-control Graphene) adopting aforesaid method to obtain has significant advantage with commercially available Graphene in size distribution, electroconductibility, stability and dispersiveness, and specific performance index sees the following form 1.
Table 1
| Commercially available Graphene | Self-control Graphene | |
| Particle diameter, nm | 100～3000 | 80～800 |
| Specific conductivity, S/cm | 500 | 700-900 |
| Decomposition temperature, DEG C | 410 | 430-480 |
| Can disperse and non-setting maximum in 1ml base oil, mg | 5 | 8-12 |
Whether note: above-mentioned base oil is following embodiment 1 base oil used, precipitate to disperse latter 60 minutes.Above-mentioned particle diameter adopts dynamic light scattering particle size analyser Dynapro Titan TC(producer: Wyatt Technology) record.Specific conductivity adopts Bel BEC-950 laboratory resistivity meter to record.Decomposition temperature adopts thermogravimetric analyzer SDT-Q600(producer: TA instrument company of the U.S.) record.Identical below.
In the present invention, described polyurea compound is without particular requirement, and the polyurea compound can commonly used for this area can be such as at least one in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein the weight ratio of two polyurea compounds, four polyurea compounds, six polyurea compounds, eight polyurea compounds can be arbitrary proportion.More preferably described polyurea compound is two polyurea compounds.
In the present invention, described two polyurea compounds preferably have following structure:
Wherein, two R
1can be the same or different, can be alkyl, cycloalkyl or aryl separately, and the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
In the present invention, described four polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, arylidene, alkylidene group or sub-cycloalkanes
The carbon number of base can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
In the present invention, described six polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
In the present invention, described eight polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
Above-mentioned polyurea compound can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A prepares.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 5-60mm
2/ s, is more preferably 10-30mm
2/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of polyurea grease as above, the method comprises: Graphene, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
In the present invention, described above for Graphene, polyurea compound and base oil, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.1-0.5 with the weight ratio of surplus base oil.
The third aspect, the invention provides the preparation method that polyurea compound is the polyurea grease of two polyureas, the method comprises:
(1) by part Graphene, organic amine and part basis oil Hybrid Heating, heat up and treat that organic amine melts completely;
(2) it is made to melt vulcabond, remainder Graphene and part basis oil Hybrid Heating;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Relative to the Graphene of 2kg, the consumption of lubricant base is preferably 60-65kg.
Fourth aspect, the invention provides and prepare the preparation method that polyurea compound is the polyurea grease of four polyureas, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-60 DEG C, add diamines, be warmed up to 80-100 DEG C, react 10-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-60 DEG C;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
5th aspect, the invention provides the preparation method that polyurea compound is the polyurea grease of six polyureas, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond 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) step (1) and step (2) gained mixing solutions are mixed and heat up react, then add diamines, reaction 10-60 minute;
(4) join in step (3) products therefrom after part basis oil and remaining vulcabond being heated to 50-70 DEG C, at 80-100 DEG C, react 10-60 minute, continue to be warmed up to 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
6th aspect, the invention provides the preparation method that polyurea compound is the polyurea grease of eight polyureas, it is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-70 DEG C, add diamines be warming up to 80-90 DEG C react 20-60 minute, again slowly add diamines, at 80-90 DEG C, react 10-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-70 DEG C;
(3) step (1) and step (2) gained mixing solutions mixed and react 10-60 minute at being warming up to 80-90 DEG C, continue to be warmed up to 180-220 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
When described polyurea compound is four polyurea compounds, six polyurea compounds or eight polyurea compounds, relative to the Graphene of 15g, the consumption of lubricant base is preferably 620-680g.
It will be understood by those skilled in the art that the amount sum of each step part basis used oil is the total amount of base oil used.Wherein, be the preparation method of the polyurea grease of two polyureas, four polyureas or eight polyureas for polyurea compound, the amount of step (1) part basis used oil and step (2) part basis used oil are preferably 1:0.1-1:0.1-1 with the weight ratio of step (3) surplus base oil used.Be the preparation method of the polyurea grease of six polyureas for polyurea compound, the amount of step (1) part basis used oil and step (2) part basis used oil are preferably 1:0.1-1:0.1-1 with the weight ratio of step (4) surplus base oil used.
Described organic amine can be monoamine, also can be diamine, or both add monoamine, also add diamines, the vulcabond added with step (2) reacts, namely be prepare polyurea compound in step (3) products therefrom, mixing polyureas can be prepared, also can prepare two independent polyurea compounds, four polyurea compounds, six polyurea compounds or eight polyurea compounds.
The method preparing mixing polyureas, without particular requirement, can adopt the thinkable various method of those skilled in the art, such as, can adopt the method for US Patent No. 3243372.
In the present invention, preparing polyurea compound is that the method for the polyurea grease of two polyurea compounds can be included in step (1) and adds part Graphene, part basis oil and monoamine, stir 2-8 minute, add again and be dissolved in vulcabond in another part base oil and remainder Graphene, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.Then be warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
In the present invention, preparing polyurea compound is that the method for the polyurea grease of four polyurea compounds can be included in step (1) and adds part Graphene, base oil, stir, add diamines, stir 2-8 minute, add monoamine, stir 2-8 minute, add and be dissolved in vulcabond in another part base oil and remainder Graphene, the mol ratio of vulcabond, diamines and monoamine is 2:1:2.Then be warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
In the present invention, preparing polyurea compound is that the method for six polyurea compounds can comprise and adds part basis oil and Graphene, stir, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, add another part base oil being dissolved with vulcabond and residue Graphene again, stir 2-8 minute, the mol ratio of added successively vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.Then be warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
In the present invention, preparing polyurea compound is that the method for eight polyurea compounds can comprise and adds part basis oil and Graphene, stir, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine, stir 2-8 minute, then add another part base oil being dissolved with vulcabond and remainder Graphene, the mol ratio of added successively vulcabond, diamines, diamines and monoamine is 4:2:1:2.Then be warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Described vulcabond structure is OCN-R
3-NCO, R
3can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, be preferably
deng.Such as, described vulcabond can be at least one in tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), hexamethylene vulcabond (HDI), dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred described monoamine is the mixture of aliphatic amide and arylamine, and the mol ratio of the two is 0.5-2:1.Described arylamine is preferably the arylamine of aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and described aliphatic amide is preferably selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Described diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
For refining process, preferably first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Be cooled to 150-160 DEG C, add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
In the present invention, the weight ratio of part Graphene and remainder Graphene is preferably 1:0.1-10, more preferably 1:0.5-5.
According to the present invention, the polyurea grease weight that the consumption of Graphene, vulcabond, various amine and base oil makes to obtain is benchmark, and the content of Graphene is 0.2-15 % by weight, is preferably 1-10 % by weight; The content of polyurea compound is 4-30 % by weight, is preferably 6-25 % by weight; The content of base oil is 65-95 % by weight, is preferably 70-93 % by weight.
7th aspect, the invention provides the polyurea grease obtained by method as above.
For the polyurea grease adopting aforesaid method to obtain, wherein the content of polyurea compound calculates according to the weight of the isocyanic ester fed intake and the amine polyurea compound of gained acquisition in theory.The content of Graphene is determined according to charging capacity.
Compared with the polyurea grease obtained with the preparation method provided by second aspect, the polyurea grease that the 7th aspect provides has better high thermal resistance, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.In following examples, dropping point adopts GB/T3498 method to record, cone penetration adopts GB/T269 method to record, oxidation stability adopts SH/T0325 method to record, Stencil oil-dividing adopts SH/T0324 method to record, non-corrosibility adopts GB/T5018 method to record, water drenches number of dropouts and adopts SH/T0109 method to record, tetra-ball machine test PB adopts SH/T0202 method to record, tetra-ball machine test PD adopts SH/T0202 method to record, copper corrosion performance adopts GB/T7326 method to record, and electroconductibility adopts SH/T0596 method to record.
Embodiment 1-6 is polyurea grease of two polyureas and preparation method thereof for illustration of polyurea compound.
Embodiment 1
The preparation of graphene oxide: 1g graphite flakes and 0.5g SODIUMNITRATE are mixed in ice bath with the 23ml vitriol oil, 3g potassium permanganate is slowly added under stirring, temperature remains on less than 10 DEG C and stirs 1h, then mixture stirs 0.5h at 35 DEG C, then adds the dilution of 50ml deionized water, releases a large amount of heat in process, carry out making temperature lower than 100 DEG C in ice bath, add 50ml water, mixture stirs 0.5h, then adds 200ml deionized water and dilute further.Add the aqueous hydrogen peroxide solution reduction potassium permanganate of 30 % by weight of 10ml afterwards.Finally, mixture mass concentration is hydrochloric acid (400ml) washing and filtering of 5%, to remove metal ion.Then acid is removed, 60 DEG C of dry 24h with 0.5L deionized water, obtained graphene oxide.
The preparation of Graphene: add 5ml hydrazine hydrate (mass concentration is 85%) after above-mentioned for 0.1g obtained graphene oxide being joined ultrasonic disperse in 100ml water (ultrasonic frequency is 30kHz) 30min, oil bath 100 DEG C reaction 24h, the powder that the black flocks finally obtained obtains after washing, suction filtration, 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 is 18mm with subtracting three line mixing oil: 64kg(100 DEG C viscosity
2/ s); Amino dodecane 5.14kg; Para-totuidine 2.49kg; MDI6.03kg; The oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg
First 1kg Graphene, 5.14kg amino dodecane and 2.49kg para-totuidine are joined in 22kg base oil, be heated to 80 DEG C, organic amine is melted completely; In 21kg base oil, add 6.03kg MDI, 1kg Graphene again, heating makes it melt; By above-mentioned two groups of solution mixing, fully stir, reaction 10min, continue to be warming up to 190 DEG C and carry out high temperature refining 20min; Add after 21kg base oil cools to 120 DEG C, add the oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg, stirs; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Embodiment 2
The preparation of graphene oxide is with embodiment 1.
The preparation of Graphene: add 5ml hydrazine hydrate (mass concentration is 85%) after the graphene oxide that 0.1g is obtained is joined ultrasonic disperse in 100ml water (ultrasonic frequency is 35kHz) 30min, oil bath 100 DEG C reaction 24h, the powder that the black flocks finally obtained obtains after washing, suction filtration, drying is Graphene, and the performance of Graphene is as shown in table 2 below.
The preparation of two urea greases:
Material component: Graphene 2kg; 500SN is 20mm with subtracting three line mixing oil: 62.4kg(100 DEG C viscosity
2/ s); Stearylamine 8.51kg; Para-totuidine 3.26kg; TDI5.51kg; The oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg.
First 0.5kg Graphene, 8.51kg stearylamine and 3.26kg para-totuidine are joined in 20.4kg base oil, be heated to 80 DEG C, organic amine is melted completely; In 21kg base oil, add 5.51kg TDI, 1.5kg Graphene again, heating makes it melt; By above-mentioned two groups of solution mixing, fully stir, reaction 15min continues to be warming up to 220 DEG C and carries out high temperature refining 5min; Add after 21kg base oil cools to 110 DEG C, add the oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg, stirs; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Embodiment 3
The preparation of graphene oxide is with embodiment 1.
The preparation of Graphene: add 5ml hydrazine hydrate (mass concentration is 85%) after the graphene oxide that 0.1g is obtained is joined ultrasonic disperse in 100ml water (ultrasonic frequency is 40kHz) 30min, oil bath 100 DEG C reaction 24h, the powder that the black flocks finally obtained obtains after washing, suction filtration, drying is Graphene, and the performance of Graphene is as shown in table 2 below.
The preparation of two urea greases:
Material component: Graphene 2kg; 500SN is 23mm with subtracting three line mixing oil: 66.4kg(100 DEG C viscosity
2/ s); Amino dodecane 4.52kg; Para-totuidine 2.19kg; TDI3.70kg; The oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg.
First 0.35kg Graphene, 4.52kg amino dodecane and 2.19kg para-totuidine are joined in 24.4kg base oil, be heated to 80 DEG C, organic amine is melted completely; In 21kg base oil, add 3.70kgTDI, 1.65kg Graphene again, heating makes it melt; By above-mentioned two groups of solution mixing, fully stir, reaction 12min continues to be warming up to 200 DEG C and carries out high temperature refining 10min; Add after 21kg base oil cools to 100 DEG C, add the oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg, stirs; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Embodiment 4
The preparation of graphene oxide is with embodiment 1.
The preparation of Graphene: add 5ml hydrazine hydrate (mass concentration is 85%) after the graphene oxide that 0.1g is obtained is joined ultrasonic disperse in 100ml water (ultrasonic frequency is 25kHz) 30min, oil bath 100 DEG C reaction 24h, the powder that the black flocks finally obtained obtains after washing, suction filtration, drying is Graphene, and the performance of Graphene is as shown in table 2 below.
The preparation of two urea greases:
Material component: Graphene 2kg; 500SN is 16mm with subtracting three line mixing oil: 63.2kg(100 DEG C viscosity
2/ s); Stearylamine 5.10kg; Para-totuidine 1.95kg; MDI4.74kg; The oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg.
First 1.5kg Graphene, 5.10kg stearylamine and 1.95kg para-totuidine are joined in 21.2kg base oil, be heated to 80 DEG C, organic amine is melted completely; In 21kg base oil, add 4.74kg MDI, 0.5kg Graphene again, heating makes it melt; By above-mentioned two groups of solution mixing, fully stir, reaction 15min continues to be warming up to 200 DEG C and carries out high temperature refining 12min; Add after 21kg base oil cools to 100 DEG C, add the T406 of oxidation inhibitor T501 and 0.64kg of 0.96kg; Stir; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Comparative example 1
Material component: except not graphene-containing, all the other are with embodiment 4
Polyurea grease is prepared according to the method for embodiment 4, unlike, do not add Graphene in the preparation process of two urea greases.Product performance are as shown in table 3.
Comparative example 2
Feed composition is with embodiment 4
Polyurea grease is prepared according to the method for embodiment 4, unlike, whole Graphene adds with oxidation inhibitor T501.The performance of polyurea grease product is as shown in table 3 below.
Comparative example 3
Except Graphene is by except the crystalline flake graphite replacement of equal in quality, all the other feed composition are with embodiment 4
Polyurea grease is prepared according to the method for embodiment 4, unlike, Graphene is replaced by the crystalline flake graphite of identical weight.The performance of polyurea grease product is as shown in table 3 below.
Embodiment 5
The preparation of Graphene is with embodiment 1
Material component: with embodiment 4
A volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add the 5.10kg stearylamine, the 1.95kg para-totuidine that dissolve with 5kg lubricating base oil, stir 6 minutes, add the 4.74kg MDI dissolved with 5kg lubricating base oil again, stir 6 minutes, 120 DEG C of constant temperature 20 minutes, obtains A system.
The preparation of polyurea grease: obtained A system, 2kg Graphene are joined in 42kg base oil and fully stir, reaction 15min continues to be warming up to 200 DEG C and carries out high temperature refining 12min; Add after 21kg base oil cools to 100 DEG C, add the T406 of oxidation inhibitor T501 and 0.64kg of 0.96kg; Stir; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Embodiment 6
Prepare polyurea grease according to the method for embodiment 4, unlike, Graphene use graphene product that to be purchased from the model specification of Ji'an, Beijing letter science and trade limited liability company be G20 (purity >95%,
Graphene size 100-200nm), gained grease product performance is as shown in table 3.
Table 2
Embodiment 7
This embodiment is mixing polyurea grease and preparation method thereof for illustration of polyurea compound.
The preparation of Graphene is with embodiment 1
The preparation of polyurea grease: first 1kg Graphene, 2.57kg amino dodecane, 4.03kg stearylamine, 0.47kg quadrol and 1.24kg para-totuidine are joined in 22kg base oil, be heated to 80 DEG C, organic amine is melted completely; In 21kg base oil, add MDI, 1kg Graphene of 6.68kg again, heating makes MDI melt; By above-mentioned two groups of solution mixing, fully stir, reaction 10min, continue to be warming up to 190 DEG C and carry out high temperature refining 20min; Add after 21kg base oil cools to 120 DEG C, add the oxidation inhibitor T501 of 0.96kg; The T406 of 0.64kg, stirs; Fat is become 2-3 time by three-roller grinding.Product performance are as shown in table 3.
Table 3
Embodiment 8-11 is polyurea grease of four polyureas and preparation method thereof for illustration of polyurea compound.
Embodiment 8
The preparation of Graphene is with embodiment 1
The preparation of four urea greases:
Material component: Graphene 15g; 500SN is 15mm with subtracting three line mixing oils 620g(100 DEG C of viscosity
2/ s); Stearylamine 80.59g; Quadrol 9.41g; MDI73.26g; 8g oxidation inhibitor T501; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 200 grams of base oils and 73.26 grams of MDI Hybrid Heating to 60 DEG C, add 9.41 grams of quadrols, be warming up to 80 DEG C, reaction 30min; Again by 7 grams of Graphenes, 210 grams of base oils and 80.59 grams of stearylamine Hybrid Heating to 60 DEG C; By above-mentioned two kinds of solution Hybrid Heating, reaction 30min; Be warming up to 210 DEG C, keep 10min, add 210 grams of base oils wherein and be cooled to 110 DEG C and add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 4.
Embodiment 9
The preparation of Graphene is with embodiment 1.
The preparation of four urea greases:
Material component: Graphene 15g; 500SN is 17mm with subtracting three line mixing oils 676g(100 DEG C of viscosity
2/ s); Stearylamine 60.03g; Quadrol 7.29g; TDI39.12g; 8g oxidation inhibitor T501; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 256 grams of base oils and 39.12 grams of TDI Hybrid Heating to 60 DEG C, add 7.29 grams of quadrols, be warming up to 80 DEG C, reaction 30min; Again by 7 grams of Graphenes, 210 grams of base oils and 60.03 grams of stearylamine Hybrid Heating to 60 DEG C; By above-mentioned two kinds of solution Hybrid Heating, reaction 30min; Be warming up to 210 DEG C, keep 10min, add 210 grams of base oils wherein and be cooled to 110 DEG C and add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 4.
Embodiment 10
The preparation of Graphene is with embodiment 1.
The preparation of four urea greases:
Material component: Graphene 15g; 500SN is 21mm with subtracting three line mixing oils 636g(100 DEG C of viscosity
2/ s); Amino dodecane 75.01g; Quadrol 11.07g; TDI61.23g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 216 grams of base oils and 61.23 grams of TDI Hybrid Heating to 60 DEG C, add 11.07 grams of quadrols, be warming up to 80 DEG C, reaction 30min; Again by 7 grams of Graphenes, 210 grams of base oils and 75.01 grams of amino dodecane Hybrid Heating to 60 DEG C; By above-mentioned two kinds of solution Hybrid Heating, reaction 30min; Be warming up to 210 DEG C, keep 10min, add 210 grams of base oils wherein and be cooled to 110 DEG C and add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 4.
Embodiment 11
The preparation of Graphene is with embodiment 1.
The preparation of four urea greases:
Material component: Graphene 15g; 500SN is 23mm with subtracting three line mixing oils 644g(100 DEG C of viscosity
2/ s); Amino dodecane 59.73g; Quadrol 9.37g; MDI69.98g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 224 grams of base oils and 69.98 grams of MDI Hybrid Heating to 60 DEG C, add 9.37 grams of quadrols, be warming up to 80 DEG C, reaction 30min; Again by 7 grams of Graphenes, 210 grams of base oils and 59.73 grams of amino dodecane Hybrid Heating to 60 DEG C; By above-mentioned two kinds of solution Hybrid Heating, reaction 30min; Be warming up to 210 DEG C, keep 10min, add 210 grams of base oils wherein and be cooled to 110 DEG C and add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 4.
Comparative example 4
Material component: 500SN is 19mm with subtracting three line mixing oils 660g(100 DEG C of viscosity
2/ s); Stearylamine 59.76g; Quadrol 7.01g; MDI55.81g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 240 grams of base oils and 55.81 grams of MDI Hybrid Heating to 60 DEG C, add 7.01 grams of quadrols, be warming up to 80 DEG C, reaction 30min; Again by 210 grams of base oils and 59.76 grams of stearylamine Hybrid Heating to 60 DEG C; By above-mentioned two kinds of solution Hybrid Heating, reaction 30min; Be warming up to 210 DEG C, keep 10min, add 210 grams of base oils wherein and be cooled to 110 DEG C and add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 4.
Table 4
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Comparative example 4 | |
| Aliphatic amide | Stearylamine | Stearylamine | Amino dodecane | Amino dodecane | Stearylamine |
| Diamines | Quadrol | Quadrol | Quadrol | Quadrol | Quadrol |
| Isocyanic ester | MDI | TDI | TDI | MDI | MDI |
| Dropping point, DEG C | >300 | >300 | >300 | >300 | >300 |
| Drawing cone in-degree, 0.1mm | 230 | 239 | 237 | 237 | 245 |
| Oxidation initial temperature, DEG C | 262 | 256 | 260 | 258 | 232 |
| Stencil oil-dividing (100 DEG C, 30h) % | 0.2 | 0.3 | 0.5 | 0.3 | 0.6 |
| Non-corrosibility (52 DEG C, 48h) | Qualified | Qualified | Qualified | Qualified | 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 | Qualified | Qualified | Qualified | Qualified | Qualified |
Embodiment 12-15 is polyurea grease of six polyureas and preparation method thereof for illustration of polyurea compound.
Embodiment 12
The preparation of Graphene is with embodiment 1
The preparation of six urea greases:
Material component: Graphene 15g; 500SN and the mixing oil 660g(100 DEG C viscosity subtracting three lines are 19mm
2/ s); Stearylamine 55g; Quadrol 12.86g; TDI54.23g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
By 8 grams of Graphenes, the mixture of 36.23 grams of TDI and 180 gram base oils is heated to 60 DEG C, again by 7 grams of Graphenes, 180 grams of base oils and 55 grams of stearylamine Hybrid Heating slowly join in above-mentioned system to 60 DEG C and by it, be warming up to 80 DEG C of reactions 30 minutes, slowly add 12.86 grams of quadrols, isothermal reaction 30min, finally by 18 grams of TDI and 150 gram base oil Hybrid Heating to 50 DEG C, join in system, constant temperature 80 DEG C reaction 30 minutes, be warming up to 120 DEG C to keep 30 minutes, then 210 DEG C are warming up to, keep 10 minutes, add 150 grams of base oil cooling downs, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501, 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 5.
Embodiment 13
The preparation of Graphene is with embodiment 1.
The preparation of six urea greases:
Material component: Graphene 15g; 500SN and the mixing oil 620g(100 DEG C viscosity subtracting three lines are 17mm
2/ s); Stearylamine 62.13g; Quadrol 14.57g; MDI86.23g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
By 8 grams of Graphenes, the mixture of 58.23 grams of MDI and 160 gram base oils is heated to 60 DEG C, again by 7 grams of Graphenes, 160 grams of base oils and 62.13 grams of stearylamine Hybrid Heating slowly join in above-mentioned system to 60 DEG C and by it, be warming up to 80 DEG C of reactions 30 minutes, slowly add 14.57 grams of quadrols, isothermal reaction 30min, finally by 28 grams of MDI and 150 gram base oil Hybrid Heating to 50 DEG C, join in system, constant temperature 80 DEG C reaction 30 minutes, be warming up to 120 DEG C to keep 30 minutes, then 210 DEG C are warming up to, keep 10 minutes, add 150 grams of base oil cooling downs, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501, 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 5.
Embodiment 14
The preparation of Graphene is with embodiment 1.
The preparation of six urea greases:
Material component: Graphene 15g; 500SN and the mixing oil 676g(100 DEG C viscosity subtracting three lines are 21mm
2/ s); Amino dodecane 42.07g; Quadrol 12.19g; TDI51.92g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
By 8 grams of Graphenes, the mixture of 34.92 grams of TDI and 188 gram base oils is heated to 60 DEG C, again by 7 grams of Graphenes, 188 grams of base oils and 42.07 grams of amino dodecane Hybrid Heating slowly join in above-mentioned system to 60 DEG C and by it, be warming up to 80 DEG C of reactions 30 minutes, slowly add 12.19 grams of quadrols, isothermal reaction 30min, finally by 17 grams of TDI and 150 gram base oil Hybrid Heating to 50 DEG C, join in system, constant temperature 80 DEG C reaction 30 minutes, be warming up to 120 DEG C to keep 30 minutes, then 210 DEG C are warming up to, keep 10 minutes, add 150 grams of base oil cooling downs, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501, 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 5.
Embodiment 15
The preparation of Graphene is with embodiment 1.
The preparation of six urea greases:
Material component: Graphene 15g; 500SN and the mixing oil 636g(100 DEG C viscosity subtracting three lines are 22mm
2/ s); Amino dodecane 48.33g; Quadrol 14.18g; MDI84.33g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
By 8 grams of Graphenes, the mixture of 56.33 grams of MDI and 168 gram base oils is heated to 60 DEG C, again by 7 grams of Graphenes, 168 grams of base oils and 48.33 grams of amino dodecane Hybrid Heating slowly join in above-mentioned system to 60 DEG C and by it, be warming up to 80 DEG C of reactions 30 minutes, slowly add 14.18 grams of quadrols, isothermal reaction 30min, finally by 28 grams of MDI and 150 gram base oil Hybrid Heating to 50 DEG C, join in system, constant temperature 80 DEG C reaction 30 minutes, be warming up to 120 DEG C to keep 30 minutes, then 210 DEG C are warming up to, keep 10 minutes, add 150 grams of base oil cooling downs, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501, 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 5.
Comparative example 5
Material component: 500SN and the mixing oil 640g(100 DEG C viscosity subtracting three lines are 19mm
2/ s); Stearylamine 53g; Quadrol 12.51g; MDI73.5g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
The mixture of 49.5 grams of MDI and 170 gram base oils is heated to 60 DEG C, again 170 grams of base oils and 55 grams of stearylamine Hybrid Heating are slowly joined in above-mentioned system to 60 DEG C and by it, be warming up to 80 DEG C of reactions 30 minutes, slowly add 12.51 grams of quadrols, isothermal reaction 30min, finally by 24 grams of MDI and 150 gram base oil Hybrid Heating to 50 DEG C, join in system, constant temperature 80 DEG C reaction 30 minutes, be warming up to 120 DEG C to keep 30 minutes, then 210 DEG C are warming up to, keep 10 minutes, add 150 grams of base oil cooling downs, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501, 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 5.
Table 5
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Comparative example 5 | |
| Aliphatic amide | Stearylamine | Stearylamine | Amino dodecane | Amino dodecane | Stearylamine |
| Diamines | Quadrol | Quadrol | Quadrol | Quadrol | Quadrol |
| Isocyanic ester | TDI | MDI | TDI | MDI | MDI |
| Dropping point, DEG C | >310 | >310 | >310 | >310 | >310 |
| Drawing cone in-degree, 0.1mm | 235 | 232 | 236 | 234 | 242 |
| Oxidation initial temperature, DEG C | 261 | 265 | 263 | 259 | 231 |
| Stencil oil-dividing 100 DEG C, 30h, % | 0.6 | 0.5 | 0.6 | 0.5 | 0.8 |
| Non-corrosibility (52 DEG C, 48h) | Qualified | Qualified | Qualified | Qualified | 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 | Qualified | Qualified | Qualified | Qualified | Qualified |
Embodiment 16-19 is polyurea grease of eight polyureas and preparation method thereof for illustration of polyurea compound.
Embodiment 16
The preparation of Graphene is with embodiment 1
The preparation of eight urea greases:
Feed composition: Graphene 15g; 500SN and subtract three line mixing oils 676g(100 DEG C of viscosity 11mm
2/ s); Stearylamine 40g; Quadrol 14.5g; TDI52.5g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 233 grams of base oils and 52.5 grams of TDI Hybrid Heating to 50 DEG C, add 9.7 grams of quadrols, be warming up to 80 DEG C, react after 30 minutes, then add 4.8 grams of quadrols, react 30 minutes, 7 grams of Graphenes, 233 grams of base oils and 40 grams of stearylamine Hybrid Heating are joined in said mixture to 60 DEG C, be warming up to 80 DEG C, react 30 minutes, continue to be warming up to 210 DEG C, keep 10 minutes, add 210 grams of base oils again, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 6.
Embodiment 17
The preparation of Graphene is with embodiment 1
The preparation of eight urea greases:
Feed composition: Graphene 15g; 500SN and subtract three line mixing oils 620g(100 DEG C of viscosity 11mm
2/ s); Stearylamine 51.5g; Quadrol 17.3g; MDI95g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 205 grams of base oils and 95 grams of MDI Hybrid Heating to 50 DEG C, add 11.3 grams of quadrols, be warming up to 80 DEG C, react after 30 minutes, then add 6 grams of quadrols, react 30 minutes, 7 grams of Graphenes, 205 grams of base oils and 51.5 grams of stearylamine Hybrid Heating are joined in said mixture to 60 DEG C, be warming up to 80 DEG C, react 30 minutes, continue to be warming up to 210 DEG C, keep 10 minutes, add 210 grams of base oils again, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 6.
Embodiment 18
The preparation of Graphene is with embodiment 1
The preparation of eight urea greases:
Feed composition: Graphene 15g; 500SN and subtract three line mixing oils 636g(100 DEG C of viscosity 11mm
2/ s); Amino dodecane 48g; Quadrol 20.5g; TDI78g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 213 grams of base oils and 78 grams of TDI Hybrid Heating to 50 DEG C, add 13.5 grams of quadrols, be warming up to 80 DEG C, react after 30 minutes, then add 7 grams of quadrols, react 30 minutes, 7 grams of Graphenes, 213 grams of base oils and 48 grams of amino dodecane Hybrid Heating are joined in said mixture to 60 DEG C, be warming up to 80 DEG C, react 30 minutes, continue to be warming up to 210 DEG C, keep 10 minutes, add 210 grams of base oils again, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 6.
Embodiment 19
The preparation of Graphene is with embodiment 1
The preparation of eight urea greases:
Feed composition: Graphene 15g; 500SN and subtract three line mixing oils 660g(100 DEG C of viscosity 11mm
2/ s); Amino dodecane 32.4g; Quadrol 14.7g; MDI75.5g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 8 grams of Graphenes, 225 grams of base oils and 75.5 grams of MDI Hybrid Heating to 50 DEG C, add 9.7 grams of quadrols, be warming up to 80 DEG C, react after 30 minutes, then add 5 grams of quadrols, react 30 minutes, 7 grams of Graphenes, 225 grams of base oils and 32.4 grams of amino dodecane Hybrid Heating are joined in said mixture to 60 DEG C, be warming up to 80 DEG C, react 30 minutes, continue to be warming up to 210 DEG C, keep 10 minutes, add 210 grams of base oils again, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 6.
Comparative example 6
Feed composition: 500SN and subtract three line mixing oils 644g(100 DEG C of viscosity 11mm
2/ s); Stearylamine 52.8g; Quadrol 18.6g; TDI68.2g; Oxidation inhibitor T5018g; Dialkyl dithiocarbamate 12g.
First by 217 grams of base oils and 68.2 grams of TDI Hybrid Heating to 50 DEG C, add 12.6 grams of quadrols, be warming up to 80 DEG C, react after 30 minutes, then add 6 grams of quadrols, react 30 minutes, 217 grams of base oils and 52.8 grams of stearylamine Hybrid Heating are joined in said mixture to 60 DEG C, be warming up to 80 DEG C, react 30 minutes, continue to be warming up to 210 DEG C, keep 10 minutes, add 210 grams of base oils again, treat that temperature is cooled to 110 DEG C, add 8 grams of oxidation inhibitor T501; 12 grams of dialkyl dithiocarbamates, stir, and become fat 2-3 time by three-roller grinding.Product performance are as shown in table 6.
Table 6
| Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Comparative example 6 | |
| Aliphatic amide | Stearylamine | Stearylamine | Amino dodecane | Amino dodecane | Stearylamine |
| Diamines | Quadrol | Quadrol | Quadrol | Quadrol | Quadrol |
| Isocyanic ester | TDI | MDI | TDI | MDI | TDI |
| Dropping point, DEG C | >330 | >330 | >330 | >330 | 315 |
| Drawing cone in-degree, 0.1mm | 246 | 242 | 243 | 245 | 269 |
| Oxidation initial temperature, DEG C | 270 | 271 | 2768 | 266 | 238 |
| Stencil oil-dividing (100 DEG C, 30h), % | 0.6 | 0.5 | 0.5 | 0.6 | 0.6 |
| Non-corrosibility (52 DEG C, 48h) | Qualified | Qualified | Qualified | Qualified | 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 | Qualified | Qualified | Qualified | Qualified | Qualified |
As can be seen from above-mentioned table 3 to the result of table 6, polyurea grease of the present invention has the performances such as excellent high thermal resistance, water resisting property and adhesivity, colloid stability, extreme pressure anti-wear, lubricating life, non-corrosibility and resistance to salt(spray)fog.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (30)
1. a polyurea grease, is characterized in that, with this polyurea grease weight for benchmark, comprises following component: the Graphene of 0.2-15 % by weight; The polyurea compound of 4-30 % by weight; The base oil of 65-95 % by weight.
2. polyurea grease according to claim 1, wherein, with this polyurea grease weight for benchmark, comprises following component: the Graphene of 1-10 % by weight; The polyurea compound of 6-25 % by weight; The base oil of 70-93 % by weight.
3. polyurea grease according to claim 1 and 2, wherein, described Graphene can disperse in 1ml base oil and non-setting maximum is 8-12mg.
4. according to the polyurea grease in claim 1-3 described in any one, wherein, the particle diameter of described Graphene is 80-800nm, and specific conductivity is 700-900S/cm, and decomposition temperature is 430-480 DEG C.
5. polyurea grease according to claim 1 and 2, wherein, described polyurea compound is at least one in two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.
6. polyurea grease according to claim 5, wherein, described polyurea compound is two polyurea compounds, and this compound has following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
3arylidene, alkylidene group or cycloalkylidene.
7. polyurea grease according to claim 6, wherein, R
1be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R
3the arylidene of 6-30, alkylidene group or cycloalkylidene.
8. polyurea grease according to claim 7, wherein, R
1the alkane of phenyl or C1-C3
The phenyl of base or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-20, R
3be
in at least one.
9. polyurea grease according to claim 5, wherein, described polyurea compound is four polyurea compounds, and this compound has following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
10. polyurea grease according to claim 5, wherein, described six polyurea compounds have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
11. polyurea greases according to claim 5, wherein, described polyurea compound is eight polyurea compounds, and this compound has following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
12. according to the polyurea grease in claim 9-11 described in any one, wherein, and R
1be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R
2be phenylene or biphenylene or carbon number be the alkylidene group of 2-12; R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
13. polyurea greases according to claim 12, wherein, R
1be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R
2be phenylene or biphenylene, or carbon number is the alkylidene group of 2-8; R
3be selected from
in at least one.
14. according to the polyurea grease in claim 1-13 described in any one, wherein, and the additive of this polyurea grease also containing 0.5-15 % by weight.
The preparation method of the polyurea grease in 15. claim 1-14 described in any one, it is characterized in that, the method comprises: Graphene, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 16. 1 kinds of polyurea greases, is characterized in that, the method comprises:
(1) by part Graphene, organic amine and part basis oil Hybrid Heating, heat up and treat that organic amine melts completely;
(2) it is made to melt vulcabond, remainder Graphene and part basis oil Hybrid Heating;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
17. preparation methods according to claim 16, wherein, described organic amine is monoamine, and the mol ratio of vulcabond and monoamine is 1:2.
The preparation method of 18. 1 kinds of polyurea greases, is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-60 DEG C, add diamines, be warmed up to 80-100 DEG C, react 20-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-60 DEG C;
(3) step (1) and step (2) gained mixing solutions are mixed and reacted, be then warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
19. preparation methods according to claim 18, wherein, the mol ratio of vulcabond, diamines and monoamine is 2:1:2.
The preparation method of 20. 1 kinds of polyurea greases, is characterized in that, the method comprises:
(1) by part Graphene, vulcabond 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) step (1) and step (2) gained mixing solutions are mixed and heat up react, then add diamines, reaction 20-60 minute;
(4) join in step (3) products therefrom after part basis oil and remaining vulcabond being heated to 50-70 DEG C, at 80-100 DEG C, react 20-60 minute, continue to be warmed up to 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
21. preparation methods according to claim 20, wherein, the mol ratio of vulcabond, monoamine, diamines and vulcabond added by each time is 2:2:2:1.
The preparation method of 22. 1 kinds of polyurea greases, is characterized in that, the method comprises:
(1) by part Graphene, vulcabond and part basis oil Hybrid Heating to 50-70 DEG C, add diamines be warming up to 80-90 DEG C react 20-60 minute, again slowly add diamines, at 80-90 DEG C, react 20-60 minute;
(2) by monoamine, remainder Graphene and part basis oil Hybrid Heating to 50-70 DEG C;
(3) step (1) and step (2) gained mixing solutions mixed and react 20-60 minute at being warming up to 80-90 DEG C, continue to be warmed up to 180-220 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
23. preparation methods according to claim 22, wherein, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
24. according to the preparation method in claim 18-23 described in any one, and wherein, the structural formula of described diamines is NH
2-R
2-NH
2, wherein, R
2the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene, preferred described diamines be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
25. according to the preparation method in claim 16-23 described in any one, and wherein, the structure of described vulcabond is OCN-R
3-NCO, R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene; Preferably, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate;
The structural formula of described monoamine is R
1-NH
2, wherein, R
1be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-20; Preferred described monoamine is the mixture of aliphatic amide and arylamine, and the mol ratio of the two is 0.5-2:1.
26. preparation methods according to claim 25, wherein, described arylamine is the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and described aliphatic amide is the aliphatic amide being selected from amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
27. according to the preparation method in claim 16-26 described in any one, and wherein, the polyurea grease weight that the consumption of Graphene, vulcabond and base oil makes to obtain is benchmark, and the content of Graphene is 0.2-15 % by weight, is preferably 1-10 % by weight; The content of polyurea compound is 4-30 % by weight, is preferably 6-25 % by weight; The content of base oil is 65-95 % by weight, is preferably 70-93 % by weight.
28. according to the preparation method in claim 15-27 described in any one, and wherein, described Graphene can disperse in 1ml base oil and non-setting maximum is 8-12mg.
29. according to the preparation method in claim 15-28 described in any one, and wherein, the particle diameter of described Graphene is 80-800nm, and specific conductivity is 700-900S/cm, and decomposition temperature is 430-480 DEG C.
30. polyurea greases obtained by the preparation method in claim 15-29 described in any one.
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| CN109401825A (en) * | 2018-10-26 | 2019-03-01 | 中国航发北京航空材料研究院 | A kind of polyureas base protective grease of containing graphene and preparation method thereof |
| CN109536262A (en) * | 2018-12-21 | 2019-03-29 | 北京圣盟科技有限公司 | A kind of containing graphene based additive lubricating grease and preparation method thereof |
| CN109705963A (en) * | 2019-02-22 | 2019-05-03 | 焦作市倍特矿业设备有限公司 | A kind of compound high stability lubricant and its preparation process |
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| CN109971528A (en) * | 2019-03-26 | 2019-07-05 | 常熟理工学院 | Composite sodium-based four polyurea grease of one kind and preparation method thereof |
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| CN105273799A (en) * | 2015-12-02 | 2016-01-27 | 国家电网公司 | Electric force compounded grease and preparation method thereof |
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| CN109536262A (en) * | 2018-12-21 | 2019-03-29 | 北京圣盟科技有限公司 | A kind of containing graphene based additive lubricating grease and preparation method thereof |
| CN109705963A (en) * | 2019-02-22 | 2019-05-03 | 焦作市倍特矿业设备有限公司 | A kind of compound high stability lubricant and its preparation process |
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| CN109971528A (en) * | 2019-03-26 | 2019-07-05 | 常熟理工学院 | Composite sodium-based four polyurea grease of one kind and preparation method thereof |
| CN110157523A (en) * | 2019-05-29 | 2019-08-23 | 常熟理工学院 | High-performance steel cord lubricating grease |
| CN110157532A (en) * | 2019-06-05 | 2019-08-23 | 常熟理工学院 | Environment-friendly type wire-rope grease and preparation method thereof |
| CN111876213A (en) * | 2020-07-17 | 2020-11-03 | 西安唐朝烯材料科技有限公司 | Salt-spray corrosion-resistant additive, lubricating grease, preparation method and application thereof |
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