CN116731763A - Polyurea lubricating grease and preparation method thereof - Google Patents
Polyurea lubricating grease and preparation method thereof Download PDFInfo
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- CN116731763A CN116731763A CN202310454005.0A CN202310454005A CN116731763A CN 116731763 A CN116731763 A CN 116731763A CN 202310454005 A CN202310454005 A CN 202310454005A CN 116731763 A CN116731763 A CN 116731763A
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- diisocyanate
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- polyurea
- base oil
- lubricating grease
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- 239000004519 grease Substances 0.000 title claims abstract description 76
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 54
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002199 base oil Substances 0.000 claims abstract description 52
- 239000002562 thickening agent Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims description 34
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 150000003973 alkyl amines Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- -1 alkyl naphthalene Chemical compound 0.000 claims description 12
- 239000002480 mineral oil Substances 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006078 metal deactivator Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000004992 toluidines Chemical class 0.000 claims description 4
- 239000013556 antirust agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- FKBYRZCVXYSLEL-UHFFFAOYSA-N 1h-triazine-4,5,6-trione Chemical class O=C1NN=NC(=O)C1=O FKBYRZCVXYSLEL-UHFFFAOYSA-N 0.000 claims description 2
- 102100039496 Choline transporter-like protein 4 Human genes 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- 101000889282 Homo sapiens Choline transporter-like protein 4 Proteins 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 239000010696 ester oil Substances 0.000 claims description 2
- 239000010685 fatty oil Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920013639 polyalphaolefin Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000008719 thickening Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 15
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 12
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000035515 penetration Effects 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- VRJULIWWOHUBFB-UHFFFAOYSA-N P(=S)(O)(O)O.C(CCC)[Zn]CCCCCCCC Chemical compound P(=S)(O)(O)O.C(CCC)[Zn]CCCCCCCC VRJULIWWOHUBFB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KONRSXDGNUZJIJ-UHFFFAOYSA-N tetradecanoic acid, 1a,2,5,5a,6,9,10,10a-octahydro-5,5a-dihydroxy-4-(hydroxymethyl)-1,1,7,9-tetramethyl-11-oxo-1h-2,8a-methanocyclopenta(a)cyclopropa(e)cyclodecen-6-yl ester Chemical compound CC1CC2C(C)(C)C2C2C=C(CO)C(O)C3(O)C(OC(=O)CCCCCCCCCCCCC)C(C)=CC31C2=O KONRSXDGNUZJIJ-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- Lubricants (AREA)
Abstract
The invention discloses polyurea lubricating grease and a preparation method thereof, wherein the polyurea lubricating grease comprises the following components in percentage by weight: 60-94% of base oil, 5-35% of thickening agent and 0.2-5% of additive; wherein the thickener is a triurea compound. The polyurea lubricating grease disclosed by the invention has excellent comprehensive properties, in particular to shear stability, thickening performance of a thickening agent and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of lubricating oil, in particular to polyurea lubricating grease and a preparation method thereof.
Background
At present, a representative variety of high-performance grease with wide market prospect firstly pushes polyurea grease, and the polyurea grease is high-quality high-temperature grease, and can be applied to mechanical equipment which continuously operates under severe conditions of high load, high speed and high temperature.
Polyurea lubricating grease is a semi-fluid lubricant with plasticity formed by thickening base oil by urea thickening agents. Compared with the traditional soap-based grease, the polyurea grease does not contain metal atoms in the molecule, and is a thickener with good thermal stability. In the long-term use process, the urea compound is an oxidation inhibitor and has no catalytic aging effect on the base oil, so that the polyurea lubricating grease has good high temperature resistance; because of the hydrophobicity of urea compounds, the polyurea lubricating grease has good water resistance, acid resistance and alkali resistance; the nitrogen atom in the molecular structure of the urea compound has non-bonded lone pair electrons, so that the electronegativity of carbonyl is strong, the urea compound has strong adsorptivity on the surface of metal, and the thicker adsorption layer prevents the metal from being directly contacted and protects the metal from being worn, thereby determining that the polyurea lubricating grease has unique performance. Its various excellent properties are summarized as follows: good thermal and oxidation stability, good low temperature properties, good corrosion and water resistance, good compatibility, long service life, good colloidal stability and lubricity. In addition, polyurea lubricating grease is particularly suitable for lubrication occasions with high temperature, high load, wide speed range and contact with poor media, and is widely applied to the steel industry, the automobile industry, electrical equipment, the aerospace industry and the like. Polyurea grease is also called as a new generation grease with the most perfect performance, and is listed as the grease with the most development prospect due to the comprehensive performance, simple manufacture and moderate price.
The polyurea lubricating grease has comprehensive performance, simple and convenient manufacture, moderate price, environmental protection and no pollution, but the polyurea lubricating grease has the defects: first, it has poor shear stability, typically softens severely at low shear rates, and the reduced cone penetration can lead to leakage and run-off of grease in the bearing, disabling lubrication, thus the polyurea grease has poor shear stability, sometimes limiting its application. Secondly, the thickening capacity of the polyurea grease thickener is poor, and compared with the traditional soap-based grease, the content of the thickener is over 50 percent higher for grease with the same consistency. In addition, polyurea grease has serious high-temperature hardening phenomenon.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides polyurea lubricating grease and a preparation method thereof, wherein the shear stability, thickening capacity and high temperature resistance of the existing polyurea lubricating grease are improved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the polyurea lubricating grease is characterized by comprising the following components in percentage by weight:
60-94% of base oil, 5-35% of thickening agent and 0.2-5% of additive;
the thickener comprises a compound of formula 1:
in the formula 1, R1 and R2 are respectively alkyl or aryl, wherein the alkyl comprises C3-C20 cycloalkyl or C2-C20 long-chain alkyl, and the aryl comprises phenyl or tolyl;
r3 and R4 are respectively
The invention also discloses a preparation method of the polyurea lubricating grease, which comprises the following steps:
mixing a base oil and a diisocyanate to obtain a first mixture, wherein the diisocyanate comprises diphenylmethane diisocyanate and/or toluene diisocyanate;
adding water with the molar quantity being 50-70% of the molar quantity of the diisocyanate into the first mixture to perform a first reaction to obtain a first product;
mixing base oil and alkylamine to obtain a second mixture, wherein the alkylamine comprises one or more than two of C2-C20 long-chain alkylamine, C3-C20 naphthenic amine, aniline and toluidine;
adding the second mixture into the first product to perform a second reaction to obtain a second product, wherein the second product contains a thickening agent, and the thickening agent is obtained by reacting the diisocyanate, the water and the alkylamine;
adding excessive water into the second product to enable excessive diisocyanate to react completely, and then heating to refine to obtain a third product;
adding base oil into the third product, and quenching and cooling the third product to obtain a fourth product;
and adding an additive into the fourth product, and grinding and dispersing to obtain the polyurea lubricating grease.
The implementation of the embodiment of the invention has the following beneficial effects:
according to the embodiment of the invention, the urea thickener is improved, the thickener with three ureido structures is adopted, and the benzene ring is used for improving the rigidity of a molecular chain structure, so that the defects of poor thickening capacity, poor shear stability and the like of the existing polyurea lubricating grease thickener are overcome.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses polyurea lubricating grease which comprises the following components in percentage by weight: 60 to 94 percent of base oil, 5 to 35 percent of thickening agent and 0.2 to 5 percent of additive.
The thickener comprises a compound of formula 1:
in the formula 1, R1 and R2 are respectively alkyl or aryl, wherein the alkyl comprises cycloalkyl with 3 to 20 carbon atoms or long-chain alkyl with 2 to 20 carbon atoms, and the aryl comprises phenyl or tolyl; r3 and R4 are respectively
In the technical scheme, firstly, the thickener comprises three ureido structures, the size of the molecular structure of the thickener can be increased, the shearing resistance is enhanced, secondly, R3 and R4 are benzene ring-containing structures, the rigidity of the thickener molecule is enhanced, the shearing resistance is further enhanced, the alkyl groups at the two ends provide flexibility and hydrophobicity, and the compatibility with base oil is enhanced. Experiments prove that the thickening agent can improve thickening capacity and shear stability.
In the above technical solution, R1 and R2 may be the same or different, and R3 and R4 may be the same or different.
Preferably, the carbon number of the long-chain alkyl is 8-18, and the carbon number of the cycloalkyl is 3-8.
Further, the cycloalkyl group may be cyclohexyl, cyclopropyl, cyclopentyl, or the like.
In a specific embodiment, the base oil may include one or more of mineral oil, polyalphaolefin oil, alkyl naphthalene, ester oil, and the like.
In a specific embodiment, the additives may include one or more of a tackifier, an antiwear extreme pressure agent, an antirust agent, a metal deactivator, an antioxidant, and the like.
Specifically, the tackifier may include one or more of polyisobutylene, ethylene-propylene rubber, polymethyl methacrylate, and the like.
The antiwear extreme pressure agent may include one or more of dialkyl dithiophosphates, dialkyl dithioformates, sulfurized fatty oils, sulfurized olefins, alkyl/aryl phosphites, alkyl/aryl phosphates, TPPT, molybdenum disulfide, graphite, zinc oxide, calcium carbonate, zirconium phosphate, and the like.
The rust inhibitor may include one or more of sulfonate, naphthalene sulfonate, imidazoline, phosphate, phosphite, and the like.
The metal deactivator may include benzotriazole derivatives and the like.
The antioxidant may include one or more of amines, phenols, triazinetriones, pentaerythritol, and dodecyl thio propyl ester.
The invention also discloses a preparation method of the polyurea lubricating grease, which comprises the following steps:
1) The base oil and the diisocyanate are mixed to obtain a first mixture, wherein the diisocyanate comprises diphenylmethane diisocyanate and/or toluene diisocyanate.
In this step, diphenylmethane diisocyanate, abbreviated as MDI, having the formula C 15 H 10 N 2 O 2 Including various isomers of 4,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, and the like.
Toluene diisocyanate, abbreviated as TDI, has a molecular formula of C 9 H 6 N 2 O 2 Including six isomers of 2,3-TDI, 2,4-TDI, 2,5-TDI, 2,6-TDI, 3,4-TDI, and 3, 5-TDI.
In this step, a liquid first mixture may be obtained by heating.
2) And adding water with the molar quantity being 50-70% of the molar quantity of the diisocyanate into the first mixture to perform a first reaction to obtain a first product.
In this step, firstly, the diisocyanate undergoes a hydrolysis reaction, and the-N=C=O groups of the diisocyanate react with water to form-NH 2 Radical and CO 2 Then, the hydrolysate is subjected to addition polymerization reaction with unreacted diisocyanate, and the sum of the hydrolysate and-NH 2 Reaction of the groups with the-n=c=o groups of the diisocyanate to give-ureido structure of NH-CO-NH-. Taking diisocyanate as diphenylmethane diisocyanate as an example, the specific reaction equation is as follows:
in one embodiment, the reaction time of the first reaction is 10min to 60min.
3) Mixing the base oil and the alkylamine to obtain a second mixture, wherein the alkylamine comprises one or more than two of C2-C20 long-chain alkylamine, C3-C20 naphthenic amine, aniline and toluidine.
Toluidine comprises three isomers, respectivelyAny one or two or more isomers may be used for the reaction.
Specifically, the cycloalkanamine may include one or two or more of cyclohexane, cyclopropane, and cyclopentane.
4) And adding the second mixture into the first product to perform a second reaction to obtain a second product, wherein the second product comprises a thickening agent shown in the formula 1, and the thickening agent is obtained by reacting diisocyanate, water and alkylamine.
In this step, the-NH of the alkylamine 2 The groups and the-n=c=o groups of the first product undergo addition polymerization to form an ureido structure of-NH-CO-NH-. Continuing to take diisocyanate as diphenylmethane diisocyanate as an example, the specific reaction equation is as follows:
in one embodiment, the second reaction time is 30min to 120min.
5) And adding excessive water into the second product to react excessive diisocyanate completely, and heating to refine to obtain a third product.
In the step, the refining temperature is 160-220 ℃ and the refining time is 10-60 min.
6) And adding base oil into the third product, and quenching and cooling the third product to obtain a fourth product.
In one embodiment, the quench cooling is reduced to below 160 ℃.
7) And adding an additive into the fourth product, and grinding and dispersing to obtain the polyurea lubricating grease.
In one embodiment, the molar ratio of diisocyanate to alkylamine is 1 to 1.5:1.
The following are specific examples.
Example 1
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
Diphenylmethane-4, 4' -diisocyanate (MDI): 4.6%
Octadecylamine (CH) 3 (CH 2 ) 16 CH 2 NH 2 )：5％
Water: 0.4%
T202 additive (butyl octyl zinc thiophosphate, antiwear extreme pressure agent): 1%
Phenyl-alpha-naphthylamine ]Antioxidants): 0.5%
T104 additive (low base number synthetic calcium sulfonate, rust inhibitor): 0.5%
T551 additive (metal deactivator): 0.2%
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and MDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added to the mixture to react for 30 minutes.
(3) Weighing octadecylamine and 40% (based on total base oil) of base oil by weight, heating to dissolve, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 2
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
MDI：7.6％
Cyclohexylamine: 3%
Water: 0.4%
T202 additive: 1%
Phenyl-alpha-naphthylamine: 0.5%
T104 additive: 0.5%
T551 additive: 0.2%
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and MDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added to the mixture to react for 30 minutes.
(3) And weighing cyclohexylamine and 40% (based on the total base oil) of the base oil by weight, heating and dissolving, adding into a reaction kettle, and reacting for 40min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 3
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
MDI：6.0％
Dodecyl amine: 4.5%
Water: 0.4%
T202：1％
Phenyl-alpha-naphthylamine: 0.5%
T104：0.5％
T551：0.2％
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and MDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added and reacted for 30 minutes.
(3) And weighing dodecylamine and 40% (based on total base oil) of the base oil by weight, heating and dissolving, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 180 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 4
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
MDI：7％
Para-toluidine: 3%
Water: 0.5%
T202：1％
Phenyl-alpha-naphthylamine: 0.5%
T104：0.5％
T551：0.2％
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and MDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added and reacted for 30 minutes.
(3) Weighing p-toluidine and 40% (based on total base oil) of base oil by weight, heating to dissolve, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 5
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
MDI：5.3％
Octadecylamine: 3%
Cyclohexylamine: 1%
Water: 0.4%
T202：1％
Phenyl-alpha-naphthylamine 0.5%
T104 0.5％
T551 0.2％
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and MDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added and reacted for 30 minutes.
(3) Weighing octadecylamine, cyclohexylamine and 40% (based on total base oil) of base oil by weight, heating for dissolving, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 160 ℃ for refining for 60min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 6
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
TDI：4％
Octadecylamine: 6%
Water: 0.4%
T202：1％
Phenyl-alpha-naphthylamine: 0.5%
T104：0.5％
T551：0.2％
The process comprises the following steps:
(1) mixing 40% (based on total base oil) by weight of base oil and TDI, adding into a reaction kettle, and heating to 80-100 ℃.
(2) 70% (based on the total water) of water was added and reacted for 30 minutes.
(3) Weighing octadecylamine and 40% (based on total base oil) of base oil by weight, heating to dissolve, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Example 7
The polyurea lubricating grease comprises the following components in percentage by weight:
mineral oil: allowance of
TDI：2％
MDI:2.5％
Octadecylamine: 5.5%
Water: 0.4%
T202：1％
Phenyl-alpha-naphthylamine: 0.5%
T104：0.5％
T551：0.2％
The process comprises the following steps:
(1) 40% (based on total base oil) by weight of base oil, MDI and TDI were mixed and added to a reaction vessel, and the temperature was raised to 60-80 ℃.
(2) 70% (based on the total water) of water was added and reacted for 30 minutes.
(3) Weighing octadecylamine and 40% (based on total base oil) of base oil by weight, heating to dissolve, adding into a reaction kettle, and reacting for 60min.
(4) And adding the rest water to react the excessive diisocyanate completely.
(5) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(6) Adding the residual oil for quenching.
(7) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
The following is a comparative example, which uses substantially the same components as the examples, except that the diisocyanate was not hydrolyzed in the preparation method, and the thickener formed was a diurea compound, specifically as follows:
comparative example 1
Comparative example 1 the components of example 1 are substantially identical, the polyurea grease comprising the following weight percent components:
mineral oil: allowance of
MDI:3.2％
Octadecylamine: 6.5%
Water: 0.05%
T202：1％
Phenyl-alpha-naphthylamine 0.5%
T104 0.5％
T551 0.2％
The process comprises the following steps:
(1) 40% by weight of base oil and MDI were mixed and added to the reaction vessel and the temperature was raised to 60-80 ℃.
(2) Weighing octadecylamine and 40% of base oil by weight, heating and dissolving, adding into a reaction kettle, and reacting for 60min.
(3) Water was then added to react the excess diisocyanate completely.
(4) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(5) Adding the residual oil for quenching.
(6) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Comparative example 2
The components of comparative example 2 and example 6 are substantially identical, and the polyurea grease comprises the following weight percent components:
mineral oil: allowance of
TDI：2.7％
Octadecylamine: 8%
Water: 0.05%
T202：1％
Phenyl-alpha-naphthylamine 0.5%
T104 0.5％
T551 0.2％
The process comprises the following steps:
(1) 40% by weight of base oil and TDI were mixed and added to a reaction vessel and the temperature was raised to 80-100 ℃.
(2) Weighing octadecylamine and 40% of base oil by weight, heating and dissolving, adding into a reaction kettle, and reacting for 60min.
(3) Water was then added to react the excess diisocyanate completely.
(4) Finally, the temperature is raised to 200 ℃ for refining for 20min.
(5) Adding the residual oil for quenching.
(6) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Comparative example 3
Comparative example 3 is essentially identical to the components of example 5, the polyurea grease comprising the following weight percent components:
mineral oil: allowance of
MDI：4.6％
Octadecylamine: 4%
Cyclohexylamine: 2%
Water: 0.05%
T202：1％
Phenyl-alpha-naphthylamine 0.5%
T104 0.5％
T551 0.2％
The process comprises the following steps:
(1) 40% by weight of base oil and MDI were mixed and added to the reaction vessel and the temperature was increased to 80-100 ℃.
(2) Weighing octadecylamine, cyclohexylamine and 40% of base oil by weight, heating and dissolving, adding into a reaction kettle, and reacting for 60min.
(3) Water was then added to react the excess diisocyanate completely.
(4) Heating to 160 ℃ and refining for 60min.
(5) Adding the residual oil for quenching.
(6) Cooling to below 100deg.C, adding additives, and grinding and dispersing to obtain grease.
Test case
The polyurea greases prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to performance tests, respectively, and the performance test standards and results are shown in Table 1.
Table 1: performance test criteria and results
* Oxidation stability (99 ℃,100h, pressure drop at 0.760 MPa/Kpa)
In table 1, the dropping point is the lowest temperature at which grease begins to drop when heated and melted, and is an index of the temperature resistance of grease. Comparative example 1 was substantially identical in composition to example 1, however, the drop point of example 1 was 255 ℃ and significantly higher than 238 ℃ of comparative example 1; comparative example 2 was substantially identical in composition to example 6, however, the drop point of example 6 was 220 ℃ higher than 215 ℃ of comparative example 2; comparative example 3 was substantially identical in composition to example 5, however, the drop point of example 5 was 282 ℃ which was significantly higher than 250 ℃ of comparative example 3. The improved high temperature resistance indicates that the phenomenon of high temperature hardening can be improved.
The working cone penetration is the depth of the cone falling into the sample under the specified load, time and temperature conditions, and is an index for measuring the consistency and hardness of the lubricating grease, and the larger the cone penetration value is, the softer the lubricating grease is, and the harder the lubricating grease is on the contrary. Comparative example 1 was substantially identical in composition to example 1, but 60 and 100000 times of example 1 had cone penetration values of 258 and 288, respectively, which were significantly lower than 320 and 370 of comparative example 1; comparative example 2 was substantially identical in composition to example 6, but 60 and 100000 times of example 6 had cone penetration of 290 and 350, respectively, which were significantly lower than 350 and 410 of comparative example 2; comparative example 3 was substantially identical in composition to example 5, but 60 and 100000 times of example 5 had cone penetration values of 238 and 259, respectively, which were significantly lower than those of 280 and 335 of comparative example 3. The significant improvement in cone penetration suggests that shear stability and thickening ability may be improved.
Compared with the prior art, the polyurea lubricating grease disclosed by the invention can improve the shear stability, thickening capacity and high temperature resistance.
It can also be seen from table 1 that: the polyurea lubricating grease disclosed by the invention is excellent in corrosion resistance, oil separation performance, hydrophobicity and oxidation stability, so that the polyurea lubricating grease disclosed by the invention has excellent comprehensive performance, in particular, shear stability, thickening performance of a thickening agent and high temperature resistance.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The polyurea lubricating grease is characterized by comprising the following components in percentage by weight:
60-94% of base oil, 5-35% of thickening agent and 0.2-5% of additive;
the thickener comprises a compound of formula 1:
in the formula 1, R1 and R2 are respectively alkyl or aryl, wherein the alkyl comprises C3-C20 cycloalkyl or C2-C20 long-chain alkyl, and the aryl comprises phenyl or tolyl;
r3 and R4 are respectively
2. The polyurea grease according to claim 1, wherein the long-chain alkyl group has a carbon number of 8 to 18 and the cycloalkyl group has a carbon number of 3 to 8.
3. The polyurea grease of claim 2, wherein the cycloalkyl group is cyclohexyl, cyclopropyl, or cyclopentyl.
4. The polyurea grease according to claim 1, wherein the base oil comprises one or more of mineral oil, polyalphaolefin oil, alkyl naphthalene, and ester oil;
the additive comprises one or more than two of tackifier, antiwear extreme pressure agent, antirust agent, metal passivating agent and antioxidant.
5. The polyurea grease according to claim 4, wherein the tackifier comprises one or more of polyisobutylene, ethylene propylene rubber, and polymethyl methacrylate;
the antiwear extreme pressure agent comprises one or more than two of dialkyl dithiophosphate, dialkyl dithioformate, vulcanized fatty oil, vulcanized olefin, alkyl/aryl phosphite, alkyl/aryl phosphate, TPPT, molybdenum disulfide, graphite, zinc oxide, calcium carbonate and zirconium phosphate;
the antirust agent comprises one or more than two of sulfonate, naphthalene sulfonate, imidazoline, phosphate and phosphite;
the metal deactivator comprises a benzotriazole derivative;
the antioxidant comprises one or more of amines, phenols, triazinetriones, pentaerythritol and dodecyl thio-propyl ester.
6. A method for preparing the polyurea lubricating grease according to any one of claims 1 to 5, comprising the following steps:
mixing a base oil and a diisocyanate to obtain a first mixture, wherein the diisocyanate comprises diphenylmethane diisocyanate and/or toluene diisocyanate;
adding water with the molar quantity being 50-70% of the molar quantity of the diisocyanate into the first mixture to perform a first reaction to obtain a first product;
mixing base oil and alkylamine to obtain a second mixture, wherein the alkylamine comprises one or more than two of C2-C20 long-chain alkylamine, C3-C20 naphthenic amine, aniline and toluidine;
adding the second mixture into the first product to perform a second reaction to obtain a second product, wherein the second product contains a thickening agent, and the thickening agent is obtained by reacting the diisocyanate, the water and the alkylamine;
adding excessive water into the second product to enable excessive diisocyanate to react completely, and then heating to refine to obtain a third product;
adding base oil into the third product, and quenching and cooling the third product to obtain a fourth product;
and adding an additive into the fourth product, and grinding and dispersing to obtain the polyurea lubricating grease.
7. The method for producing a polyurea grease according to claim 6, wherein the molar ratio of the diisocyanate to the alkylamine is 1 to 1.5:1.
8. The method for preparing polyurea grease according to claim 6, wherein the reaction time of the first reaction is 10min to 60min.
9. The method for preparing polyurea grease according to claim 6, wherein the reaction time of the second reaction is 30min to 120min.
10. The method for preparing polyurea grease according to claim 6, wherein the refining temperature is 160 ℃ to 220 ℃ and the refining time is 10min to 60min.
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| EP0103864A2 (en) * | 1982-09-17 | 1984-03-28 | Chuo Yuka Co., Ltd. | Triurea grease compositions |
| US6214778B1 (en) * | 1995-08-24 | 2001-04-10 | The Lubrizol Corporation | Polyurea-thickened grease composition |
| CN1723270A (en) * | 2003-01-06 | 2006-01-18 | 日本精工株式会社 | Grease composition for automobile electrical equipment auxiliary device and prelubricated rolling bearing using the grease composition |
| CN101693851A (en) * | 2009-09-30 | 2010-04-14 | 中国石油化工股份有限公司 | Synthetic high-temperature lubricating grease and production method thereof |
| CN102417843A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Hexaurea lubricating grease and preparation method thereof |
| CN105008503A (en) * | 2013-03-14 | 2015-10-28 | 出光兴产株式会社 | Grease composition for bearing |
| CN112521998A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Low-noise polyurea lubricating grease composition and preparation method thereof |
-
2023
- 2023-04-25 CN CN202310454005.0A patent/CN116731763A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103864A2 (en) * | 1982-09-17 | 1984-03-28 | Chuo Yuka Co., Ltd. | Triurea grease compositions |
| US6214778B1 (en) * | 1995-08-24 | 2001-04-10 | The Lubrizol Corporation | Polyurea-thickened grease composition |
| CN1723270A (en) * | 2003-01-06 | 2006-01-18 | 日本精工株式会社 | Grease composition for automobile electrical equipment auxiliary device and prelubricated rolling bearing using the grease composition |
| CN101693851A (en) * | 2009-09-30 | 2010-04-14 | 中国石油化工股份有限公司 | Synthetic high-temperature lubricating grease and production method thereof |
| CN102417843A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Hexaurea lubricating grease and preparation method thereof |
| CN105008503A (en) * | 2013-03-14 | 2015-10-28 | 出光兴产株式会社 | Grease composition for bearing |
| CN112521998A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Low-noise polyurea lubricating grease composition and preparation method thereof |
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