CN109679713B - Lithium-based lubricating grease and preparation method thereof - Google Patents
Lithium-based lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN109679713B CN109679713B CN201710969256.7A CN201710969256A CN109679713B CN 109679713 B CN109679713 B CN 109679713B CN 201710969256 A CN201710969256 A CN 201710969256A CN 109679713 B CN109679713 B CN 109679713B
- Authority
- CN
- China
- Prior art keywords
- group
- formula
- branched
- straight
- grease
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004519 grease Substances 0.000 title claims abstract description 98
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002199 base oil Substances 0.000 claims abstract description 48
- 239000002562 thickening agent Substances 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims abstract 10
- -1 hydrocarbon radicals Chemical class 0.000 claims description 156
- 125000000217 alkyl group Chemical group 0.000 claims description 146
- 229910052739 hydrogen Inorganic materials 0.000 claims description 92
- 150000003254 radicals Chemical class 0.000 claims description 92
- 239000001257 hydrogen Substances 0.000 claims description 88
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 50
- 125000003342 alkenyl group Chemical group 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 150000002431 hydrogen Chemical class 0.000 claims description 29
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 27
- 239000013556 antirust agent Substances 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 239000012964 benzotriazole Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 11
- 125000004434 sulfur atom Chemical group 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- 238000007127 saponification reaction Methods 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 150000001565 benzotriazoles Chemical class 0.000 description 49
- 229920000098 polyolefin Polymers 0.000 description 42
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 16
- 239000004166 Lanolin Substances 0.000 description 16
- 229940039717 lanolin Drugs 0.000 description 16
- 235000019388 lanolin Nutrition 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 229920002367 Polyisobutene Polymers 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 101100407037 Oryza sativa subsp. japonica PAO6 gene Proteins 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- FPLIHVCWSXLMPX-UHFFFAOYSA-M lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- KFXTTZQGCNRYEN-UHFFFAOYSA-N 2-n-octadecylpropane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCNC(C)CN KFXTTZQGCNRYEN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GLSMCDMRGPEDIC-UHFFFAOYSA-N dihydroxy-(5-methylundecan-5-ylsulfanyl)-sulfanylidene-lambda5-phosphane Chemical compound C(CCC)C(CCCCCC)(C)SP(O)(O)=S GLSMCDMRGPEDIC-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000010193 shuanglong Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
- C07F9/65188—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
- C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Abstract
The invention provides lithium-based lubricating grease and a preparation method thereof. The lithium-based lubricating grease disclosed by the invention comprises the following components by taking the total weight of the lubricating grease as a reference: benzotriazole derivatives, lithium-based thickeners, rust inhibitors, and a major amount of a lubricating base oil. The lithium-based lubricating grease disclosed by the invention has the advantages of lower friction coefficient, excellent extreme pressure wear resistance, excellent oxidation stability, excellent corrosion resistance, excellent antirust performance, excellent colloid stability and excellent mechanical stability, and can be suitable for severe working conditions such as high speed, high load, excessive water and the like.
Description
Technical Field
The invention relates to lubricating grease, in particular to lithium-based lubricating grease.
Background
The lithium-based lubricating grease is a multi-effect lubricating grease which is fastest in development, largest in current production and widest in application field in the 40 th century. The american grease society uses the proportion of lithium-based grease in a country as a measure of the state of the art in the grease industry. The lithium-based lubricating grease has the advantages of good colloid stability, mechanical stability, long service cycle, wide range and the like, is an ideal multi-purpose and long-service-life lubricating grease, but the lithium-based lubricating grease also has some defects: such as poor oxidation resistance, poor abrasion resistance, and poor water resistance.
Lithium-based greases are traditionally produced by reacting 12-hydroxystearic acid or stearic acid with lithium hydroxide in a base oil, followed by heating and saponification to give the final product, as in US 3980572.
In order to improve the performance of the lithium-based lubricating grease, the formula and the process of the lithium-based lubricating grease are improved to different degrees. For example, CN 101126045A prepares a lithium-based lubricating grease with lighter color and better oxidation resistance through improving the preparation process; CN 1718702A selects high-viscosity mineral oil to prepare high extreme pressure lithium-based lubricating grease; CN 101880581A improves the reaction temperature, and improves the service life and water resistance of the product.
With the increasing of parameters such as power, speed, precision and the like of modern mechanical equipment, the working load is higher and higher, the service environment is more and more harsh, so that the abrasion and the service life of mechanical parts are greatly influenced, and in order to improve the lubricating performance of the lubricating grease and prolong the service life of the equipment, an anti-wear and anti-friction agent needs to be added into the lubricating grease to reduce the frictional resistance between frictional surfaces and prevent the abrasion and the scuffing of materials.
Disclosure of Invention
The invention provides lithium-based lubricating grease and a preparation method thereof.
Specifically, the present invention relates to the following aspects.
1. The lithium-based lubricating grease comprises the following components by taking the total weight of the lubricating grease as a reference: benzotriazole derivatives, lithium-based thickeners, rust inhibitors and a major amount of lubricating base oil, wherein the benzotriazole derivatives have the structure shown in the general formula (I):
in the general formula (I), the radical R' is selected from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), or is selected from C1-20Hydrocarbyl and C3-20A linear or branched heteroalkyl radical, preferably selected from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), more preferably C10-25A linear or branched alkyl group; n is selected from an integer from 0 to 10, preferably from an integer from 0 to 5, more preferably 0; n radicals R0Are the same or different from each other and are each independently selected from C1-10Straight or branched alkylene, preferably independently selected from C2-5A linear or branched alkylene group; n +2 groups A, which are the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C1-25The hydrocarbon group and the hydrocarbon group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably independently selected from the group consisting of hydrogen, the group represented by the formula (I-1), the group represented by the formula (I-2), and C 1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25The polyisobutenyl group having a linear or branched alkenyl group and a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) is preferably independently selected from the group consisting of hydrogen, the group represented by the formula (I-1), the group represented by the formula (I-2) and C1-4A linear or branched alkyl group, preferably each independently selected from hydrogen, a group represented by formula (I-1) and a group represented by formula (I-2), provided that at least one of the n +2 groups A is a group represented by formula (I-1) and at least one of the n +2 groups A is a group represented by formula (I-2); when at least one of said groups A is C10-25Straight or branched alkyl, C10-25When the alkenyl group is a linear or branched alkenyl group or a hydrocarbon group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), the group R' may also be hydrogen,
in the general formula (I-1) and the general formula (I-2), the group R5And R6Are the same or different from each other and are each independently selected from C1-20Hydrocarbyl (especially C)1-20Straight or branched alkyl), preferably each independently selected from C1-15Straight or branched alkyl, more preferably each independently selected from C3-12A linear or branched alkyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom, preferably both groups X are sulfur atoms and both groups Y are oxygen atoms; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C 1-20Hydrocarbyl, preferably independently selected from hydrogen and C1-20Straight or branched chain alkyl, more preferably each independently selected from hydrogen and C1-6Straight or branched chain alkyl, more preferably both hydrogen; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-20Hydrocarbyl, preferably independently selected from hydrogen and C1-10Straight or branched alkyl, more preferably R1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched alkyl (preferably C)1-6Linear or branched alkyl), the other being hydrogen, the linear or branched heteroalkyl meaning that the carbon chain structure of the linear or branched alkyl is selected from-O-, -S-and-NR- (wherein the group R is selected from H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) of1-4Straight-chain or branched alkyl, preferably selected from H and methyl).
2. A grease according to any one of the preceding aspects, wherein the benzotriazole derivative is selected from the following specific compounds or mixtures of any two or more thereof:
3. the lithium-based lubricating grease comprises the following components by weight: a benzotriazole derivative produced by a process comprising the step of reacting a phosphorus compound represented by formula (I-A), an amine compound represented by formula (I-B), and a benzotriazole compound represented by formula (I-C) in the presence of an aldehyde represented by formula (I-D),
Wherein the radical R' is selected from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), or is selected from C1-20Hydrocarbyl and C3-20A linear or branched heteroalkyl radical, preferably selected from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), more preferably C10-25A linear or branched alkyl group; n is selected from an integer from 0 to 10, preferably from an integer from 0 to 5, more preferably 0; n radicals R0Are the same or different from each other and are each independently selected from C1-10Straight or branched alkylene, preferably independently selected from C2-5A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C1-25The hydrocarbyl group and the hydrocarbyl group with the number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably respectively and independently selected from hydrogen and C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25The linear or branched alkenyl group and the polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably each independently selected from hydrogen and C1-4Straight-chain or branched alkyl, with the proviso that at least two of the n +2 groups A' represent hydrogen; when at least one of said groups A' is C 10-25Straight or branched alkyl, C10-25Straight chainOr branched alkenyl or hydrocarbyl having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), said group R' may also be hydrogen; radical R5And R6Are the same or different from each other and are each independently selected from C1-20Hydrocarbyl (especially C)1-20Straight or branched alkyl), preferably each independently selected from C1-15Straight or branched alkyl, more preferably each independently selected from C3-12A linear or branched alkyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom, preferably both groups X are sulfur atoms and both groups Y are oxygen atoms; the radical R' is selected from hydrogen and C1-20Hydrocarbyl, preferably selected from hydrogen and C1-20Straight or branched alkyl, more preferably selected from hydrogen and C1-6Straight or branched alkyl, more preferably hydrogen; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-20A hydrocarbyl group, preferably each independently selected from hydrogen and C1-10Straight or branched alkyl, more preferably R1And R4Are each hydrogen, R2And R3Is one of C1-10Straight or branched alkyl (preferably C)1-6Linear or branched alkyl), the other being hydrogen, the linear or branched heteroalkyl meaning that the carbon chain structure of the linear or branched alkyl is selected from-O-, -S-and-NR- (wherein the group R is selected from H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) of 1-4Straight-chain or branched alkyl, preferably selected from H and methyl).
4. The production process according to any one of the preceding aspects, wherein the reaction time of the reaction is 0.1 to 24 hours, preferably 0.5 to 6 hours, and the reaction temperature of the reaction is 0 to 250 ℃, preferably 60 to 120 ℃.
5. The production process according to any one of the preceding aspects, wherein the molar ratio of the phosphorus compound represented by the formula (I-A) to the amine compound represented by the formula (I-B) is 1:0.1 to 10, preferably 1:0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1:0.1 to 10, preferably 1:0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1:1 to 10, preferably 1:2 to 4.
6. A grease according to any one of the preceding aspects, wherein the benzotriazole derivative constitutes from 0.01% to 10% (preferably from 0.1% to 5%) of the total mass of the grease; the lithium-based thickening agent accounts for 5-35% (preferably 8-20%) of the total mass of the lubricating grease; the antirust agent accounts for 0.1-10% (preferably 0.5-2%) of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
7. The grease according to any one of the preceding aspects, wherein the lithium-based thickener can be formed by reacting a polymeric acid with lithium hydroxide, wherein the polymeric acid is a C12-C25 fatty acid and/or a hydroxy fatty acid, and can be one or more of lauric acid, myristic acid, palmitic acid, stearic acid and 12-hydroxystearic acid, and is preferably stearic acid and/or 12-hydroxystearic acid; the lubricating base oil is one or more of mineral oil, vegetable oil and synthetic oil; the mineral oil can be one or more of paraffin base oil, intermediate base oil and naphthenic base oil, and preferably has a kinematic viscosity of 5-60mm at 100 ℃ 2A lubricating base oil of which the kinematic viscosity at 100 ℃ is from 10 to 30mm is most preferred2Lubricating base oil/s; the vegetable oil can be one or more of castor oil, rapeseed oil, peanut oil and soybean oil; the synthetic oil can be one or more of poly alpha-olefin oil, ester oil, fluorine oil and silicone oil; the lubricating base oil preferably has a kinematic viscosity of 5-60mm at 100 DEG C2A lubricating base oil of which the kinematic viscosity at 100 ℃ is from 10 to 30mm is most preferred2Lubricating base oil per second.
The antirust agent is selected from one or more of organic carboxylic acid type antirust agents, organic carboxylate type antirust agents, ester type antirust agents, organic amine type antirust agents and sulfur-containing or nitrogen-containing heterocyclic type antirust agents, preferably the ester type antirust agents, and for example, one or more of calcium lanolin, magnesium lanolin, benzene-80 and barium soap of oxidized petroleum ester can be selected.
In the grease composition of the present invention, the content of each component can be calculated according to the amount of the charged components. Wherein, the content of the lithium-based thickener is 100 percent multiplied by the weight of the lithium polymer/the total weight of the grease.
8. The method for preparing the lithium-based grease according to any one of the preceding aspects, comprising: the lithium-based thickener and the lubricating base oil in any aspect are uniformly mixed, are refined at the constant temperature of 230 ℃ at 180 ℃, are cooled, and are added with the benzotriazole derivative and the antirust agent in any aspect to obtain a finished product.
A preferred method of preparing a lithium-based grease comprises: mixing and heating part of base oil and high molecular acid, heating to 80-105 ℃, adding an aqueous solution of lithium hydroxide, performing saponification reaction, heating to 190-220 ℃ after complete reaction, refining, adding the rest base oil, cooling to 100-120 ℃, and adding the benzotriazole derivative and the antirust agent to obtain a finished product.
The high molecular acid is C12-C25 fatty acid and/or hydroxy fatty acid.
Among them, the temperature of the saponification is preferably 80 to 95 ℃ and the time of the saponification is preferably 0.2 to 1.5 hours, more preferably 0.5 to 1 hour.
The water content in the aqueous solution of lithium hydroxide is such that the saponification reaction proceeds smoothly. In general, it is 0.1 to 10 times by weight, preferably 0.8 to 8 times by weight, the amount of lithium hydroxide used.
The refining time is preferably 5 to 25 minutes.
According to the invention, the fraction of base oil: the remaining base oil 40-75: 25-60.
Other operations and conditions of the preparation process of the present invention can be carried out with reference to the prior art.
The lithium-based lubricating grease disclosed by the invention has the advantages of lower friction coefficient, excellent extreme pressure wear resistance, oxidation stability, corrosion resistance, antirust performance, colloid stability and mechanical stability, improves the water-leaching resistance, and can be used under severe working conditions of high speed, high load, excessive water and the like.
Technical effects
The benzotriazole derivative according to the present invention contains no metal element, is not liable to generate ash and deposits, and is an environmentally friendly lubricant additive.
The benzotriazole derivatives according to the present invention show significantly improved antiwear properties and extreme pressure properties as compared with prior art lubricating oil additives, and are effective in improving the antiwear properties and load-bearing capacity of lubricating oils.
The benzotriazole derivative according to the present invention, in a preferred embodiment, exhibits excellent abrasion resistance and, at the same time, further exhibits excellent thermal oxidation stability (thermal stability). This is not the case with the prior art lubricating oil additives.
The benzotriazole derivative according to the present invention, in a preferred embodiment, exhibits excellent anti-wear properties while further exhibiting excellent anti-corrosion properties. This is not the case with the prior art lubricating oil additives.
According to the benzotriazole derivative of the present invention, in a preferred embodiment, while exhibiting excellent anti-wear properties, it further exhibits excellent rust inhibitive properties. This is not the case with the prior art lubricating oil additives.
According to the benzotriazole derivative of the present invention, in a preferred embodiment, while exhibiting excellent anti-wear properties, it further exhibits excellent friction reducing properties. Which is not simultaneously possessed by the lubricating oil additives of the prior art.
The method for preparing the benzotriazole derivative has the characteristics of simple process, no waste gas discharge, less waste water, safety, environmental protection and the like.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or a synonym thereof, directed to a material, substance, method, step, device, or component, the subject matter from which the heading is derived encompasses those conventionally used in the art as presented in the present application, but also includes those not currently in use, but which would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
In the context of the present invention, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
In the context of the present invention, the term "hydrocarbyl" has the meaning conventionally known in the art and includes straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, cycloalkenyl, aryl, or combinations thereof. As the hydrocarbon group, a linear or branched alkyl group, a linear or branched alkenyl group, an aryl group, or a combination thereof is preferable. Specific examples of the hydrocarbon group include C1-30The hydrocarbon group is more specifically exemplified by C1-30Straight or branched alkyl, C 2-30Straight-chain or branched alkenyl, C3-20Cycloalkyl, C3-20Cycloalkenyl radical, C6-20Aryl or a combination thereof.
In the context of the present specification as C1-4Examples of the straight-chain or branched alkyl group include methyl, ethyl and propyl groups, and C is2-4Examples of the straight-chain or branched alkenyl group include a vinyl group, an allyl group, and an propenyl group.
In the context of the present invention, the term "linear or branched heteroalkyl" refers to a linear or branched alkyl groupIs substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from-O-, -S-and-NR- (wherein the group R is selected from H and C)1-4Straight-chain or branched alkyl, preferably selected from H and methyl). It is preferable from the viewpoint of structural stability that, when plural, any two of the hetero groups are not directly bonded to each other. It is apparent that the hetero group is not at the end of the carbon chain of the linear or branched alkyl group or the linear or branched heteroalkyl group. It is expressly stated here that, although the interruptions may be present (for example by a heterogroup-NR-and R represents C)1-4Linear or branched alkyl) may result in the linear or branched heteroalkyl group having a different total number of carbon atoms than the linear or branched alkyl group, but for convenience, the number of carbon atoms in the linear or branched heteroalkyl group prior to the interruption is still used to refer to the number of carbon atoms in the linear or branched heteroalkyl group after the interruption.
In the context of the present specification, the number average molecular weight Mn is determined by Gel Permeation Chromatography (GPC), unless otherwise specified.
In the context of the present specification, any reference to Gel Permeation Chromatography (GPC) or measurement conditions of a GPC profile, unless otherwise specified, is: the instrument adopts a Waters 2695 type gel permeation chromatographic analyzer of the Waters company in America, tetrahydrofuran is adopted as a mobile phase, the flow rate is 1mL/min, the temperature of a chromatographic column is 35 ℃, the outflow time is 40min, and the mass fraction of a sample is 0.16-0.20%.
Finally, unless otherwise explicitly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless not otherwise generally recognized by those of skill in the art.
According to the invention, firstly, the benzotriazole derivative is shown as a general formula (I).
According to the bookAccording to the invention, in the general formula (I), the radical R' is selected from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in formula (I), the radical R' is chosen from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
According to a particular embodiment of the invention, in formula (I), the radical R' is chosen from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000.
According to one embodiment of the invention, in formula (I), the radical R' represents C10-25Straight or branched chain alkyl. Here, as the C10-25Straight or branched alkyl, such as C10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.
According to one embodiment of the invention, in formula (I), the radical R' represents C10-25Straight or branched alkenyl. Here, as the C10-25Straight-chain or branched alkenyl, for example, C10-25Examples of the linear alkenyl group include n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.
According to a particular embodiment of the invention, in formula (I), the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500. Examples of the polyolefin include ethylene, propylene and C4-C10A homo-polymerization of α -olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or a polyolefin obtained by copolymerization of two or more of these olefins, with Polyisobutylene (PIB) being more preferred.
According to the invention, in the general formula (I), n is selected from integers from 0 to 10.
According to a particular embodiment of the invention, in formula (I), n is chosen from integers from 0 to 5.
According to a particular embodiment of the invention, in formula (I), n is 0, 1, 2 or 3, such as 0.
According to the invention, in the general formula (I), n radicals R 0Are the same or different from each other and are each independently selected from C1-10Straight or branched chain alkylene.
According to a particular embodiment of the invention, in the general formula (I), n radicals R0Are the same or different from each other and are each independently selected from C2-5Straight or branched chain alkylene. Here, as the C2-5Examples of the straight-chain or branched alkylene group include an ethylene group and a propylene group.
According to the invention, in the general formula (I), n +2 groups A, equal to or different from each other, are each independently selected from hydrogen, a group represented by formula (I-1), a group represented by formula (I-2), C1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in the general formula (I), n +2 radicals A, which are identical to or different from one another, are each, independently of one anotherIs selected from hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25Linear or branched alkenyl groups and polyisobutenyl groups having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in the general formula (I), n +2 groups A, equal to or different from each other, are each independently selected from hydrogen, the group represented by formula (I-1), the group represented by formula (I-2) and C 1-4Straight or branched chain alkyl.
According to a particular embodiment of the invention, in the general formula (I), n +2 groups A, equal to or different from each other, are each independently selected from hydrogen, the group represented by formula (I-1) and the group represented by formula (I-2).
According to one embodiment of the invention, in the general formula (I), the group a represents hydrogen.
According to one embodiment of the invention, in the general formula (I), the group A represents C1-4Straight or branched chain alkyl.
According to one embodiment of the invention, in the general formula (I), the group A represents C10-25Straight or branched chain alkyl. Here, as the C10-25Straight or branched alkyl, such as C10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.
According to one embodiment of the invention, in the general formula (I), the group A represents C 10-25Straight-chain or branched alkenyl. Here, the C is defined as10-25Straight-chain or branched alkenyl, for example, C10-25Examples of the straight chain alkenyl group include a n-6-dodecenyl group, a n-6-tridecenyl group, a n-7-tetradecenyl group, a n-7-pentadecenyl group, a n-8-hexadecenyl group, a n-8-heptadecenyl group, and a n-9-decadecenyl groupOctenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl, and the like.
According to a particular embodiment of the invention, in formula (I), the group A represents a hydrocarbon radical having an average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having an average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500. Examples of the polyolefin include ethylene, propylene and C 4-C10A homo-polymerization of α -olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or a polyolefin obtained by copolymerization of two or more of these olefins, with Polyisobutylene (PIB) being more preferred.
According to the invention, in the general formula (I), at least one of the n +2 groups A is a group represented by the formula (I-1), and at least one of the n +2 groups A is a group represented by the formula (I-2). Specifically, for example, when n is 0, in the general formula (I), one of 2 groups A is a group represented by the formula (I-1), and the other is a group represented by the formula (I-2). Or, specifically for example, when n is 1, in the general formula (I), one of 3 said groups A is a group represented by the formula (I-1) and the other two are groups represented by the formula (I-2), or two of 3 said groups A are groups represented by the formula (I-1) and the other is a group represented by the formula (I-2). Or, for example, when n is 1, in the general formula (I), one of 3 said groups A is a group represented by formula (I-1), one is a group represented by formula (I-2), one is hydrogen, C1-4Straight or branched alkyl, C 10-25Straight or branched alkyl, C10-25Linear or branched alkenyl or a number average molecular weight Mn of300-3000 hydrocarbyl.
According to a particular embodiment of the invention, in formula (I), when at least one of said n +2 groups A represents said C10-25Straight or branched alkyl, said C10-25The radical R' may also be hydrogen or hydrogen in the case of a linear or branched alkenyl radical or in the case of a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. In other words, according to this particular embodiment of the invention, in formula (I), at least one of the group A and the group R' must represent said C10-25Straight or branched alkyl, said C10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.
According to the invention, in the general formula (I-1), the radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in formula (I-1), the radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-10Straight or branched chain alkyl. Here, as the C1-10Straight-chain or branched alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to a particular embodiment of the present invention, in formula (I-1), R1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen. Here, as the C1-10Straight-chain or branched alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to a particular embodiment of the present invention, in the general formula (I-1), R1、R3And R4Are each hydrogen, R2Is C1-10Straight or branched chain alkyl. Here, as the C1-10Straight-chain or branched alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to the invention, in formula (I-1), the group R' is chosen from hydrogen and C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in formula (I-1), the radical R' is chosen from hydrogen and C1-20Straight or branched chain alkyl.
According to a particular embodiment of the invention, in formula (I-1), the radical R' is chosen from hydrogen and C1-6Straight or branched chain alkyl. Here, the C is defined as1-6Straight-chain or branched alkyl, such as C 1-6More specific examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.
According to a particular embodiment of the invention, in formula (I-1), the radical R' represents hydrogen.
According to the invention, in the general formula (I-2), the radical R5And R6Are the same or different from each other and are each independently selected from C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in formula (I-2), the radical R5And R6Are the same or different from each other and are each independently selected from C1-20Straight or branched chain alkyl.
According to a particular embodiment of the invention, in formula (I-2), the radical R5And R6Are the same or different from each other and are each independently selected from C1-15Straight or branched chain alkyl.
According to a particular embodiment of the invention, in formula (I-2), the radical R5And R6Are the same or different from each other and are each independently selected from C3-12Straight or branched chain alkyl. Here, as the C3-12Specific examples of the linear or branched alkyl group include n-propyl, n-butyl, n-hexyl, n-decyl, n-dodecyl, isobutyl, isopentyl, isooctyl, isodecyl, isododecyl, 2-ethyl-n-hexyl, 2-ethyl-n-heptyl, 2-ethyl-n-octyl, and 2-ethyl-n-decyl.
According to the invention, in the general formula (I-2), the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom.
According to a particular embodiment of the invention, in formula (I-2), both groups X are sulfur atoms and both groups Y are oxygen atoms.
According to the invention, in formula (I-2), the group R' is chosen from hydrogen and C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in formula (I-2), the radical R' is chosen from hydrogen and C1-20Straight or branched chain alkyl.
According to a particular embodiment of the invention, in formula (I-2), the radical R' is chosen from hydrogen and C1-6Straight or branched chain alkyl. Here, as the C1-6Straight-chain or branched alkyl, such as C1-6Examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.
According to a particular embodiment of the invention, in formula (I-2), the radical R' represents hydrogen.
According to the present invention, the benzotriazole derivative may be present, produced or used in the form of a single (pure) compound, or in the form of a mixture (in any ratio) of two or more thereof, without affecting the achievement of the effects of the present invention.
According to the present invention, the benzotriazole derivative can be produced, for example, by the following production method.
According to the present invention, the production method comprises a step of reacting the phosphorus compound represented by the formula (I-A), the amine compound represented by the formula (I-B), and the benzotriazole compound represented by the formula (I-C) in the presence of the aldehyde represented by the formula (I-D). This step will be referred to simply as the reaction step hereinafter.
According to the invention, in the general formula (I-A), the radical R5And R6Are the same or different from each other and are each independently selected from C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in the formula (I-A), the radical R5And R6Are the same or different from each other and are each independently selected from C1-20Straight or branched chain alkyl.
According to a particular embodiment of the invention, in the formula (I-A), the radical R5And R6Are the same or different from each other and are each independently selected from C1-15Straight or branched chain alkyl.
According to a particular embodiment of the invention, in the formula (I-A), the radical R5And R6Are the same or different from each other and are each independently selected from C3-12Straight or branched chain alkyl. Here, as the C3-12Specific examples of the linear or branched alkyl group include n-propyl, n-butyl, n-hexyl, n-decyl, n-dodecyl, isobutyl, isopentyl, isooctyl, isodecyl, isododecyl, 2-ethyl-n-hexyl, 2-ethyl-n-heptyl, 2-ethyl-n-octyl, and 2-ethyl-n-decyl.
According to the invention, in the general formula (I-A), the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulphur atom.
According to a particular embodiment of the invention, in formula (I-A), both groups X are sulfur atoms and both groups Y are oxygen atoms.
According to the present invention, the phosphorus compound represented by the formula (I-A) may be produced by a commercially available method as it is or by a method conventionally known in the art, and is not particularly limited. Further, the phosphorus compound represented by the formula (I-A) may be used alone or in combination of two or more.
According to the invention, in the general formula (I-B), the radical R' is chosen from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in formula (I-B), the radical R' is chosen from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
According to a particular embodiment of the invention, in formula (I-B), the radical R' is chosen from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000.
According to one embodiment of the invention, in the general formula (I-B), the radical R' represents C10-25Straight or branched chain alkyl. Here, the C is defined as10-25Straight or branched alkyl, such as C10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.
According to one embodiment of the invention, in formula (I-B), the radical R' represents C10-25Straight-chain or branched alkenyl. Here, as the C10-25Straight-chain or branched alkenyl, for example, C10-25Straight chain alkenyl groups, or there may be mentioned, for example, n-6-dodecenyl, n-6-tridecenyl and n-7-dodecenylTetraenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.
According to a particular embodiment of the invention, in the formula (I-B), the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500.
In the context of the present specification, the polyolefin residues may be saturated (present as long-chain alkyl groups) or may contain an amount of olefinic double bonds in the polymer chain (such as those remaining during the polyolefin production process), depending on the starting polyolefin species or the production process, but this does not affect the achievement of the effect of the present invention, and the present invention is not intended to make explicit this amount.
According to a particular embodiment of the invention, the polyolefin is, for example, ethylene, propylene or C4-C10Homo-polymerization of alpha-olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or polyolefins obtained by copolymerization of two or more of these olefins.
According to a particular embodiment of the invention, as the polyolefin, polybutene is more preferred. As used herein, unless otherwise indicated, the term "polybutene" broadly includes polymers obtained by the homopolymerization of 1-butene or isobutylene, as well as polymers obtained by the copolymerization of two or three of 1-butene, 2-butene and isobutylene. Commercial products of such polymers may also contain negligible amounts of other olefinic components, but this does not affect the practice of the invention.
According to a particular embodiment of the present invention, as the polyolefin, Polyisobutylene (PIB) or highly reactive polyisobutylene (HR-PIB) is further preferred. In such polyisobutenes, at least 20% by weight (preferably at least 50% by weight, more preferably at least 70% by weight) of the total terminal olefinic double bonds are provided by methylvinylidene groups.
According to the invention, in the general formula (I-B), n is selected from integers from 0 to 10.
According to a particular embodiment of the invention, in formula (I-B), n is chosen from integers from 0 to 5.
According to a particular embodiment of the present invention, in the general formula (I-B), n is 0, 1, 2 or 3, and a specific example thereof is 0.
According to the invention, in the general formula (I-B), n radicals R0Are the same or different from each other and are each independently selected from C1-10Straight or branched chain alkylene.
According to a particular embodiment of the invention, in the formula (I-B), n radicals R0Are the same or different from each other and are each independently selected from C2-5Straight or branched chain alkylene. Here, as the C2-5Examples of the straight-chain or branched alkylene group include an ethylene group and a propylene group.
According to the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C 1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25Linear or branched alkenyl groups and polyisobutenyl groups having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen and C1-4Straight or branched chain alkyl.
According to one embodiment of the invention, in the general formula (I-B), the group A' represents hydrogen.
According to one embodiment of the invention, in the formula (I-B), the group A' represents C1-4Straight or branched chain alkyl.
According to one embodiment of the invention, in the formula (I-B), the group A' represents C10-25Straight or branched chain alkyl. Here, as the C10-25Straight or branched alkyl, such as C10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.
According to one embodiment of the invention, in the formula (I-B), the group A' represents C10-25Straight-chain or branched alkenyl. Here, as the C10-25Straight-chain or branched alkenyl, for example, C10-25Examples of the linear alkenyl group include n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.
According to a particular embodiment of the invention, in the formula (I-B), the radical A' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500.
In the context of the present specification, depending on the starting polyolefin species or the manufacturing process, the polyolefin residues may be saturated (present as long chain alkyl groups) or may contain a certain amount of olefinic double bonds in the polymer chain (such as remaining during the polyolefin manufacturing process), but this does not affect the achievement of the effect of the present invention, nor does the present invention intend to make this amount explicit.
According to a particular embodiment of the invention, the polyolefin is, for example, ethylene, propylene or C4-C10Homo-polymerization of alpha-olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or polyolefins obtained by copolymerization of two or more of these olefins.
According to a particular embodiment of the invention, as the polyolefin, polybutene is more preferred. As used herein, unless otherwise indicated, the term "polybutene" broadly includes polymers obtained by the homopolymerization of 1-butene or isobutylene, as well as polymers obtained by the copolymerization of two or three of 1-butene, 2-butene and isobutylene. Commercial products of such polymers may also contain negligible amounts of other olefinic components, but this does not affect the practice of the invention.
According to a particular embodiment of the invention, as the polyolefin, Polyisobutylene (PIB) or highly reactive polyisobutylene (HR-PIB) is further preferred. In such polyisobutenes, at least 20% by weight (preferably at least 50% by weight, more preferably at least 70% by weight) of the total terminal olefinic double bonds are provided by methylvinylidene groups.
According to the invention, in the general formula (I-B), at least two of said n +2 groups A' represent hydrogen. For example, when n is 0, 2 of the groups A' in formula (I-B) each represent hydrogen. Or, by way of specific example, when n is 1, in formula (I-B), two of the 3 said groups A' represent hydrogen and the other represents hydrogen, C1-4Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl or hydrocarbyl with a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in formula (I-B), when at least one of said n +2 groups A' represents said C10-25Straight or branched alkyl, said C10-25The group R' may also be hydrogen or hydrogen when the alkenyl group is linear or branched or when the hydrocarbyl group has a number average molecular weight Mn of 300-3000. In other words, according to this particular embodiment of the invention, in formula (I-B), at least one of the groups A 'and R' must represent said C 10-25Straight or branched alkyl, said C10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.
According to the present invention, the amine compound represented by the formula (I-B) may be produced by a method conventionally known in the art without any particular limitation, as it is, or by a commercially available product. In addition, the amine compound represented by the formula (I-B) may be used alone or in combination of two or more.
According to the invention, in the general formula (I-C), the radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in the formula (I-C), the radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-10Straight or branched chain alkyl. Here, as the C1-10Straight-chain or branched alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to a particular embodiment of the invention, in the general formula (I-C), R1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen. Here, as the C 1-10Straight or branched chain alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to a particular embodiment of the invention, in the general formula (I-C), R1、R3And R4Are all hydrogen, R2Is C1-10Straight or branched chain alkyl. Here, the C is defined as1-10Straight-chain or branched alkyl, such as C1-6Straight or branched alkyl, more specific examples being C1-6More specific examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl, and n-hexyl groups.
According to the present invention, the benzotriazole compound represented by the formula (I-C) may be produced by a method conventionally known in the art without any particular limitation, as it is, using a commercially available product. Further, the benzotriazole compound represented by the formula (I-C) may be used alone or in combination of two or more.
According to the invention, in the general formula (I-D), the radical R' is chosen from hydrogen and C1-20A hydrocarbyl group.
According to a particular embodiment of the invention, in the general formula (I-D), the radical R' is chosen from hydrogen and C1-20Straight or branched chain alkyl.
According to a particular embodiment of the invention, in the general formula (I-D), the radical R' is chosen from hydrogen and C 1-6Straight or branched chain alkyl. Here, the C is defined as1-6Straight or branched chain alkyl, such as C1-6Examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.
According to a particular embodiment of the invention, in the general formula (I-D), the radical R' represents hydrogen.
According to the present invention, the aldehyde represented by the formula (I-D) may be produced by a commercially available product as it is or by a method conventionally known in the art, and is not particularly limited. In addition, the aldehyde represented by the formula (I-D) may be used alone or in combination of two or more.
According to a particular embodiment of the invention, the aldehyde represented by formula (I-D) is formaldehyde. The formaldehyde may be, for example, an aqueous formaldehyde solution, paraformaldehyde or paraformaldehyde, and is not particularly limited.
According to the present invention, in the reaction step, the reaction time of the reaction is generally 0.1 to 24 hours, preferably 0.2 to 12 hours, and most preferably 0.5 to 6 hours, for example, but is not limited thereto in some cases.
According to the present invention, in the reaction step, for example, the reaction temperature of the reaction is generally 0 to 250 ℃, preferably 20 to 180 ℃, and most preferably 60 to 120 ℃, but is not limited thereto in some cases.
According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the amine compound represented by the formula (I-B) is generally 1:0.1 to 10, preferably 1:0.5 to 5.0, more preferably 1:0.6 to 1.5, but is not limited thereto in some cases.
According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is generally 1:0.1 to 10, preferably 1:0.5 to 5.0, more preferably 1:0.6 to 1.5, but is not limited thereto in some cases.
According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is generally 1:1 to 10, preferably 1:1.5 to 6.0, more preferably 1:2 to 4, but is not limited thereto in some cases.
According to the present invention, in the reaction step, the manner of feeding each reaction raw material is not particularly limited, and may be, for example, one-time feeding, batch feeding or dropwise feeding.
According to the present invention, the order of feeding the reaction raw materials in the reaction step is not particularly limited, and specific examples thereof include the order of feeding the phosphorus compound represented by the formula (I-A), the amine compound represented by the formula (I-B), the benzotriazole compound represented by the formula (I-C), and the aldehyde represented by the formula (I-D), and the feeding may be carried out in any order.
According to the present invention, the reaction step may be carried out in the presence of a diluent and/or a solvent, or may be carried out without a diluent and/or a solvent.
According to the present invention, in the reaction step, for example, as the diluent, one or more selected from the group consisting of polyolefin, mineral base oil and polyether can be given. Examples of the mineral base oil include API group I, II, and III mineral lubricant base oils, more specifically, mineral lubricant base oils having a viscosity of 20 to 120 centistokes (cSt) at 40 ℃ and a viscosity index of at least 50, and still more specifically, mineral lubricant base oils having a viscosity of 28 to 110 centistokes (cSt) at 40 ℃ and a viscosity index of at least 80. Examples of the polyolefin include ethylene, propylene and C4-C10One or more of polyolefins obtained by homopolymerization of alpha-olefins or copolymerization of two or more of these olefins, preferably one or more of Polyalphaolefins (PAO) having a viscosity of 2 to 25 centistokes (cSt) at 100 ℃ (preferably having a viscosity of 6 to 10 centistokes (cSt) at 100 ℃). Wherein, as said C4-C10Examples of the α -olefin include n-butene, isobutene, n-pentene, n-hexene, n-octene, and n-decene. In addition, the number average molecular weight Mn of the polyolefin is generally 500-3000, preferably 500-2500, and most preferably 500-1500. Examples of the polyether include polymers obtained by reacting an alcohol with an epoxide. Examples of the alcohol include ethylene glycol and/or 1, 3-propanediol. Examples of the epoxide include ethylene oxide and/or propylene oxide. In addition, the number average molecular weight Mn of the polyether is generally 500-3000, preferably 700-3000, and most preferably 1000-2500. These diluents may be used alone or in combination of two or more.
According to the bookIn the present invention, in the reaction step, for example, the solvent may be C2-10Aliphatic nitriles (e.g. acetonitrile, etc.), C6-20Aromatic hydrocarbons (such as benzene, toluene, xylene and cumene), C6-10Alkanes (e.g. hexane, cyclohexane and petroleum ether), C1-6Aliphatic alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1, 2-dichlorobenzene), C3-10Ketones (e.g. acetone, butanone and methyl isobutyl ketone) or C3-10Amides (such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone) and the like. These solvents may be used alone or in combination of two or more.
According to a particular embodiment of the present invention, the diluent and/or solvent may be added at any stage of the reaction step in an amount conventional in the art, and is not particularly limited.
According to the invention, it is evident that said reaction step is generally carried out under protection of an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas, and are not particularly limited.
According to the present invention, after the end of the process for producing the benzotriazole derivative, the benzotriazole derivative is obtained by removing water and a solvent, if any, from the finally obtained reaction mixture by any conventionally known means. Accordingly, the present invention also relates to a benzotriazole derivative produced by the aforementioned method for producing a benzotriazole derivative of the present invention.
According to the present invention, by the aforementioned method for producing a benzotriazole derivative, a single benzotriazole derivative can be produced as a reaction product, or a mixture of a plurality of benzotriazole derivatives, or a mixture of one or more of the benzotriazole derivatives and the diluent (if used) can be produced. These reaction products are all intended for the present invention, and the difference in the form of their existence does not affect the achievement of the effects of the present invention. Accordingly, these reaction products are collectively referred to as benzotriazole derivatives without distinction in the context of this specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further isolate a benzotriazole derivative of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.
The benzotriazole derivatives of the present invention are particularly useful for the manufacture of or as antiwear agents, especially lubricating oil antiwear agents. The antiwear agent of the present invention not only has excellent extreme pressure antiwear performance, but also has one or more excellent performances of thermal oxidation stability, corrosion resistance, antirust performance and antifriction performance. According to a particularly preferred embodiment of the present invention, the anti-wear agent has not only excellent extreme pressure anti-wear properties but also excellent thermal oxidation stability, anti-corrosion properties, anti-rust properties and anti-friction properties.
According to the present invention, the anti-wear agent comprises any of the aforementioned benzotriazole derivatives of the present invention (or mixtures thereof in any proportion) or a benzotriazole derivative produced according to the aforementioned method for producing a benzotriazole derivative of the present invention.
According to the present invention, in order to manufacture the anti-wear agent, the aforementioned diluent or other components conventionally used in the art for manufacturing anti-wear agents may be further added to the benzotriazole derivative. In this case, the diluents may be used alone or in combination of two or more. Of course, if the benzotriazole derivatives of the present invention already contain a certain amount of the diluent after the preparation as described above, then the amount of the diluent added can be correspondingly reduced, and even used as an anti-wear agent without further addition of the diluent, as will be apparent to those skilled in the art.
In general, in the anti-wear agent of the present invention, the benzotriazole derivative accounts for 5% to 100%, preferably 30% to 90%, by mass of the total mass of the anti-wear agent.
According to the present invention, in order to manufacture the anti-wear agent, for example, the benzotriazole derivative, the diluent, and the other components (if used) may be mixed at 20 ℃ to 60 ℃ for 1h to 6h, without particular limitation.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
The performance evaluation in examples and comparative examples was carried out in accordance with the following method.
The dropping point is measured by a GB/T3498 method;
the cone penetration is measured by a GB/T269 method;
the oxidation stability is measured by SH/T0325 method;
the method for measuring the oil separation of the steel mesh adopts an SH/T0324 method;
the GB/T5018 method is adopted for measuring the corrosion resistance;
the SH/T0109 method is adopted for measuring the water leaching loss;
test for four-ball machineB、PDAdopting an SH/T0202 method;
the GB/T7326 method is adopted for measuring the corrosion performance of the copper sheet;
the SH/T0204 method is adopted for measuring the antiwear property.
TABLE 1 sources of raw materials
Name of raw materials | Manufacturer of the product |
500SN base oil | Yanshan petrochemical |
150BS base oil | Shuanglong Co Ltd |
PAO6 synthetic hydrocarbon oil | Mobil Corp. |
500SN base oil | Mobil Corp. |
12-Hydroxystearic acid | Zhengzhou Jinbang chemical Co., Ltd |
Stearic acid | Suzhou Yuan Tairun chemical Co., Ltd |
Lithium hydroxide | Zhengzhou bannuo chemical products Co Ltd |
Lanolin magnesium | Chemical Co., Ltd of Jinan Boao |
Lanolin calcium | Chemical Co., Ltd of Jinan Boao |
Example 1
Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 100mL of toluene were added to a 500mL four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 48.4 g (200mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 6 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-1.
Product characterization data are as follows:
1H NMR(300MHz,CDCl3):δ0.88(3H),1.03(12H),1.06-1.91(53H),2.34-3.46(10H),3.54-4.57(12H),5.23-6.11(2H),7.19-8.08(4H);
C49H96N6O4P2S4calcd for C57.50, H9.45, N8.21, O6.25, P6.05, S12.53; measurement value: c57.42, H9.43, N8.16, O6.35, P6.10, S12.54.
Preparation of lithium grease:
the raw material components are as follows: 795kg of 500SN base oil (viscosity of 10mm at 100℃)2S); 28kg of lithium hydroxide; 176kg of stearic acid; 5kg of lanolin magnesium; 20kg of benzotriazole derivative (M-1).
Firstly, 600kg of base oil and 176kg of stearic acid are added into a grease making kettle, and the mixture is heated and stirred. Adding 56kg of lithium hydroxide aqueous solution (containing 28kg of lithium hydroxide and 28g of water) for saponification reaction for 30min when the temperature is increased to 85 ℃, and continuously heating to 190 ℃ for high-temperature refining for 5 min; adding 195kg of base oil, cooling to 120 ℃, adding 5kg of lanolin magnesium and 20kg of benzotriazole derivative (M-1), and uniformly stirring; the fat is formed by grinding 2 times by means of a three-roll mill, marked as Z-1.
The grease obtained in this example had a composition, based on the weight of the grease, of: 18 wt% lithium stearate; 79.5 wt% lubricating base oil; lanolin magnesium 0.5 wt%; 2% by weight of the benzotriazole derivative (M-1).
Example 2
Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 17.93 g (150mmol) of benzotriazole and 120mL of toluene were added to a 500mL four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 24.2 g (100mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 8 hours at a constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-2.
Product characterization data are as follows:
1H NMR(300MHz,CDCl3):δ0.88(3H),1.03-1.95(51H),2.45-3.30(9H),3.54-4.32(7H),5.58-6.20(4H),7.19-8.08(8H);
C47H82N9O2PS2calcd for C62.70, H9.18, N14.00, O3.55, P3.44, S7.12; measurement value: c62.81, H9.22, N13.85, O3.56, P3.41, S7.15.
Preparation of lithium grease:
the raw material components are as follows: 910kg of 150BS base oil (viscosity of 31mm2/s at 100 ℃); 12kg of lithium hydroxide; 78kg of 12-hydroxystearic acid; 5kg of lanolin calcium; 5kg of benzotriazole derivative (M-2).
Firstly, 610kg of base oil and 78kg of 12-hydroxystearic acid are added into a grease making kettle, and the mixture is heated and stirred. Adding 120kg of lithium hydroxide aqueous solution (containing 12kg of lithium hydroxide and 108kg of water) for saponification reaction for 60min when the temperature is increased to 95 ℃, and continuously heating to 220 ℃ for high-temperature refining for 20 min; adding 300kg of base oil, cooling to 100 ℃, adding 5kg of lanolin calcium and 5kg of benzotriazole derivative (M-2), and uniformly stirring; the fat is formed by grinding 3 times by means of a three-roll mill, marked as Z-2.
The grease obtained in this example had a composition, based on the weight of the grease, of: 8 wt% of lithium 12-hydroxystearate; 91 wt% lubricating base oil; lanolin calcium 0.5 wt%; 0.5% by weight of a benzotriazole derivative (M-2).
Example 3
Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 100mL of toluene were added into a 500mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 48.4 g (200mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 6 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-3.
Product characterization data are as follows:
1H NMR(300MHz,CDCl3):δ0.88(3H),1.03(12H),1.06-1.91(53H),2.34-3.46(10H),3.54-4.28(12H),5.23-5.77(2H),7.19-8.08(4H);
C49H96N6O4P2S4calcd for C57.50, H9.45, N8.21, O6.25, P6.05, S12.53; measurement value: c57.62, H9.49, N8.13, O6.22, P6.09, S12.45.
Preparation of lithium grease:
the raw material components are as follows: 850kg (viscosity at 100 ℃ C. of 5.8 mm) of PAO6 synthetic hydrocarbon oil2S); 18kg of lithium hydroxide; 117kg of 12-hydroxystearic acid; 20kg of lanolin calcium; 10kg (M-3) of benzotriazole derivative.
348kg of base oil and 117kg of 12-hydroxystearic acid are added into a grease making kettle, and the mixture is heated and stirred. Heating to 90 deg.C, adding 108kg of lithium hydroxide aqueous solution (containing 18kg of lithium hydroxide and 90kg of water) for saponification for 50 min; continuously heating to 210 ℃ for refining at high temperature for 10 min; adding 502kg of base oil, cooling to 110 ℃, adding 20kg of lanolin calcium and 10kg of benzotriazole derivatives (M-3), and uniformly stirring; the fat is formed by grinding 3 times by means of a three-roll mill, marked as Z-3.
The grease obtained in this example had a composition, based on the weight of the grease, of: 12 wt% of lithium 12-hydroxystearate; 85 wt% of lubricating base oil; 2% by weight of lanolin calcium; 1% by weight of benzotriazole derivative (M-3).
Example 4
In a 500ml four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 133.81 g (410mmol) of octadecylpropylenediamine and 25.8 g (860mmol) of paraformaldehyde, 55.89 g (380mmol) of 5-ethylbenzotriazole and 134.15 g (450mmol) of n-butyl 1-methylheptyl dithiophosphoric acid were added, stirred rapidly, and heated to 110 ℃ for reaction for 4 hours. And after the reaction is finished, removing residual water by reduced pressure distillation, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, which is marked as M-4.
Product characterization data are as follows:
1H NMR(300MHz,CDCl3):δ0.88(6H),1.03-1.93(57H),2.43-2.74(8H),3.46-4.10(4H),4.24-4.63(2H),5.31-6.20(2H),7.19-7.82(3H);
C43H82N5O2PS2calcd for C64.86, H10.38, N8.80, O4.02, P3.89, S8.05; measurement value: c64.57, H10.05, N7.54, O4.37, P4.42, S9.05.
Preparation of lithium grease:
the raw material components are as follows: 800kg (viscosity at 100 ℃ C. is 13 mm) of 500SN and 150BS mixed oil2S); 25kg of lithium hydroxide; 157kg of stearic acid; 10kg of lanolin magnesium; 30kg of benzotriazole derivative (M-4).
500kg of base oil and 157kg of stearic acid are added into a grease making kettle, and the mixture is heated and stirred. Adding 100kg of lithium hydroxide aqueous solution (containing 25kg of lithium hydroxide and 7kg of water) for saponification reaction for 40min when the temperature is increased to 85 ℃ from 5 ℃, and continuously heating to 200 ℃ for high-temperature refining for 15 min; adding 300kg of base oil, cooling to 120 ℃, adding 10kg of lanolin magnesium and 30kg of benzotriazole derivative (M-4), and uniformly stirring; the fat is formed by grinding 2 times by means of a three-roll mill, marked as Z-4.
The grease obtained in this example had a composition, based on the weight of the grease, of: 16 wt% of lithium stearate; 80 wt% of lubricating base oil; lanolin magnesium 1 wt%; 3% by weight of a benzotriazole derivative (M-4).
Comparative example 1
Preparation of comparative grease:
a lithium-based grease was prepared according to the method of example 4, except that no benzotriazole derivative was added during the preparation. The resulting comparative grease was labeled DZ-1.
Comparative example 2
Under the protection of nitrogen, 35.04 g (130mmol) of octadecylamine, 9 g (300mmol) of paraformaldehyde, 29.78 g (250mmol) of benzotriazole and 100mL of toluene were added into a 250mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 90 ℃ and reacted at constant temperature for 6 hours. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, and filtering to remove impurities to obtain the product, wherein the label is D-1.
Product characterization data were as follows:
1H NMR(300MHz,CDCl3):δ0.88(3H),1.25-1.51(32H),3.27(2H),5.55-6.24(4H),7.19-8.08(8H);
C32H49N7calcd for C72.27, H9.29, N18.44; measurement value: c72.95, H10.32, N16.73.
Preparation of comparative grease:
a comparative grease was prepared as in example 4, except that the benzotriazole derivative used was D-1 and the comparative grease produced was designated as DZ-2.
The lithium-based lubricating grease and the comparative lubricating grease prepared in the above way are subjected to performance evaluation of dropping point, penetration degree, oxidation stability, steel mesh oil separation, corrosion resistance, water spray loss, four-ball machine test, copper sheet corrosion performance and wear resistance respectively, and the results are shown in table 2.
TABLE 2 grease Properties
As can be seen from the results in table 2, the lithium-based grease of the present invention has a low friction coefficient, and excellent wear resistance, extreme pressure performance, oxidation resistance, corrosion resistance, rust resistance, high temperature resistance, water resistance and adhesion, colloid stability, and the like.
Claims (23)
1. The lithium-based lubricating grease comprises the following components by taking the total weight of the lubricating grease as a reference: benzotriazole derivatives, lithium-based thickeners, rust inhibitors and a major amount of lubricating base oil, wherein the benzotriazole derivatives have the structure shown in the general formula (I):
in the general formula (I), the radical R' is selected from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 10; n radicals R0Are the same or different from each other and are each independently selected from C1-10A linear or branched alkylene group; n +2 groups A, which may be the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000, provided that at least one of the n +2 groups A is a group represented by the formula (I-1) and at least one of the n +2 groups A is a group represented by the formula (I-2); when at least one of said groups A is C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl or hydrocarbon radicals having a number average molecular weight Mn of 300-3000, the radicals R' may also be hydrogen,
in the general formula (I-1) and the general formula (I-2), the group R5And R6Are the same or different from each other and are each independently selected from C1-20A hydrocarbyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C 1-20A hydrocarbyl group; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-20A hydrocarbon radical, said linear or branched heteroalkyl referring to a radical obtained by interrupting the carbon chain structure of a linear or branched alkyl radical by one or more heteroatomic radicals selected from the group consisting of-O-, -S-and-NR-, wherein the radical R is selected from the group consisting of H and C1-4Straight or branched chain alkyl.
2. Grease according to claim 1,
in the general formula (I), the radical R' is selected from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 5; n radicals R0Are the same or different from each other and are each independently selected from C2-5A linear or branched alkylene group; n +2 groups A, which may be the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25A linear or branched alkenyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000;
in the general formula (I-1) and the general formula (I-2), the group R5And R6Are the same or different from each other and are each independently selected from C1-15A linear or branched alkyl group; both groups X are sulfur atoms and both groups Y are oxygen atoms; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C 1-20A linear or branched alkyl group; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-10A linear or branched alkyl group;
the straight or branched heteroalkyl group means a group obtained by interrupting the carbon chain structure of the straight or branched alkyl group with 1 to 5 hetero atom groups selected from the group consisting of-O-, -S-, and-NR-.
3. Grease according to claim 1,
in the general formula (I), the radical R' is selected from C10-25A linear or branched alkyl group; n is 0; n +2 groups A, which are the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2) and C1-4A linear or branched alkyl group;
in the general formula (I-1) and the general formula (I-2), the group R5And R6Are the same or different from each other and are each independently selected from C3-12A linear or branched alkyl group; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C1-6A linear or branched alkyl group; r1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen.
4. Grease according to claim 1, characterized in that in formula (I), the group R' is chosen from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
5. Grease as claimed in claim 1, characterized in that the number average molecular weight Mn is 500-2000.
6. Grease according to claim 1, characterized in that the number average molecular weight Mn is 500-1500.
8. the lithium-based lubricating grease comprises the following components by weight: a benzotriazole derivative, a lithium-based thickener, a rust inhibitor, and a major amount of a lubricating base oil, the benzotriazole derivative being produced by a method comprising the step of reacting a phosphorus compound represented by formula (I-A), an amine compound represented by formula (I-B), and a benzotriazole compound represented by formula (I-C) in the presence of an aldehyde represented by formula (I-D),
wherein the radical R' is selected from C1-25Hydrocarbyl radical, C3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 10; n radicals R0Are the same or different from each other and are each independently selected from C1-10A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C1-25A hydrocarbyl group having a number average molecular weight Mn of 300-3000, provided that at least two of said n +2 groups A' represent hydrogen; when at least one of said groups A' is C 10-25Straight or branched alkyl, C10-25The radical R' may also be hydrogen when it is a linear or branched alkenyl radical or a hydrocarbon radical having a number-average molecular weight Mn of 300-3000; radical R5And R6Are the same or different from each other and are each independently selected from C1-20A hydrocarbyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom; the radical R' is selected from hydrogen and C1-20A hydrocarbyl group; radical R1、R2、R3、R4The straight or branched heteroalkyl being the same or different from each other, means that the carbon chain structure of the straight or branched alkyl is interrupted by one or more hetero atom groups selected from-O-, -S-and-NR-)Group, wherein the group R is selected from H and C1-4Straight or branched chain alkyl.
9. Grease according to claim 8,
wherein the radical R' is selected from C10-25Straight or branched alkyl, C10-25Straight-chain or branched alkenyl, C10-25Straight-chain or branched alkynyl, C10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 5; n radicals R0Are the same or different from each other and are each independently selected from C2-5A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25A linear or branched alkenyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; radical R 5And R6Are the same or different from each other and are each independently selected from C1-15A linear or branched alkyl group; both groups X are sulfur atoms and both groups Y are oxygen atoms; the radical R' is selected from hydrogen and C1-20A linear or branched alkyl group; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C1-10A linear or branched alkyl group;
the straight or branched heteroalkyl group means a group obtained by interrupting the carbon chain structure of the straight or branched alkyl group with 1 to 5 hetero atom groups selected from the group consisting of-O-, -S-, and-NR-.
10. Grease according to claim 8,
wherein the radical R' is selected from C10-25A linear or branched alkyl group; n is 0; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen and C1-4A linear or branched alkyl group; radical R5And R6Are the same or different from each other and are each independently selected from C3-12A linear or branched alkyl group; the radical R' is selected from hydrogen and C1-6A linear or branched alkyl group; r1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen.
11. Grease according to claim 8, characterized in that in formula (I) the group R' is chosen from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
12. Grease according to claim 8, characterized in that the number average molecular weight Mn is 500-2000.
13. Grease as claimed in claim 8, characterized in that the number average molecular weight Mn is 500-1500.
14. The grease of claim 8, wherein the reaction time of the reaction is 0.1 to 24 hours and the reaction temperature of the reaction is 0 to 250 ℃.
15. The grease of claim 8, wherein the reaction time of the reaction is 0.5 to 6 hours and the reaction temperature of the reaction is 60 to 120 ℃.
16. The grease of claim 8, wherein the molar ratio of the phosphorus compound represented by formula (I-a) to the amine compound represented by formula (I-B) is 1:0.1 to 10; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1: 0.1-10; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1:1 to 10.
17. The grease of claim 8, wherein the molar ratio of the phosphorus compound represented by formula (I-a) to the amine compound represented by formula (I-B) is 1: 0.6-1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1:0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1: 2-4.
18. Grease according to any of claims 1-17, characterized in that the benzotriazole derivative constitutes from 0.01% to 10% of the total mass of the grease; the lithium-based thickening agent accounts for 5-35% of the total mass of the lubricating grease; the antirust agent accounts for 0.1-10% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
19. Grease according to any of claims 1-17, characterized in that the benzotriazole derivative constitutes from 0.1 to 5% of the total mass of the grease; the lithium-based thickening agent accounts for 8-20% of the total mass of the lubricating grease; the antirust agent accounts for 0.5-2% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
20. The grease as claimed in any one of claims 1 to 17 wherein the lithium-based thickener is formed by reacting a polymeric acid with lithium hydroxide; the antirust agent is one or more of an organic carboxylic acid antirust agent, an organic carboxylate antirust agent, an ester antirust agent, an organic amine antirust agent and a sulfur-containing or nitrogen-containing heterocyclic antirust agent; the lubricating base oil is one or more of mineral oil, vegetable oil and synthetic oil.
21. The grease of claim 20, wherein the polymeric acid is a C12-C25 fatty acid and/or a hydroxy fatty acid.
22. A method of preparing a lithium-based grease as defined in any one of claims 1 to 21 comprising: uniformly mixing the lithium-based thickener and the lubricating base oil as described in one of claims 1 to 21, refining at a constant temperature of 230 ℃, cooling, adding the benzotriazole derivative and the rust inhibitor as described in one of claims 1 to 21, and grinding into grease.
23. A method of preparing a grease of claim 20 or 21, comprising: mixing and heating part of lubricating base oil and high molecular acid, heating to 80-105 ℃, adding an aqueous solution of lithium hydroxide, performing saponification reaction, heating to 190-220 ℃ after complete reaction, refining, adding the rest lubricating base oil, cooling to 100-120 ℃, adding the benzotriazole derivative and the antirust agent, and grinding into grease.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710969256.7A CN109679713B (en) | 2017-10-18 | 2017-10-18 | Lithium-based lubricating grease and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710969256.7A CN109679713B (en) | 2017-10-18 | 2017-10-18 | Lithium-based lubricating grease and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109679713A CN109679713A (en) | 2019-04-26 |
CN109679713B true CN109679713B (en) | 2022-06-28 |
Family
ID=66183237
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710969256.7A Active CN109679713B (en) | 2017-10-18 | 2017-10-18 | Lithium-based lubricating grease and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109679713B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102504913A (en) * | 2011-11-17 | 2012-06-20 | 天津市澳路浦润滑油有限公司 | Extreme pressure antiwear additive and preparation method and application thereof |
CN106590819A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Compound lithium-based lubricating grease and preparing method thereof |
CN106590822A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Complex lithium-calcium-based lubricating grease and preparation method thereof |
-
2017
- 2017-10-18 CN CN201710969256.7A patent/CN109679713B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102504913A (en) * | 2011-11-17 | 2012-06-20 | 天津市澳路浦润滑油有限公司 | Extreme pressure antiwear additive and preparation method and application thereof |
CN106590819A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Compound lithium-based lubricating grease and preparing method thereof |
CN106590822A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Complex lithium-calcium-based lubricating grease and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN109679713A (en) | 2019-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107312036B (en) | Benzotriazole derivative, and preparation method and application thereof | |
JP5835530B2 (en) | Dialkyl polysulfide, method for producing dialkyl polysulfide, extreme pressure additive and lubricating fluid composition. | |
CN109679713B (en) | Lithium-based lubricating grease and preparation method thereof | |
CN109679731B (en) | Composite aluminum-based lubricating grease and preparation method thereof | |
CN109679753B (en) | Bentonite lubricating grease and preparation method thereof | |
CN109679719B (en) | Gasoline engine lubricating oil composition and preparation method thereof | |
CN109679708B (en) | Ethanol engine lubricating oil composition and preparation method thereof | |
CN109679711B (en) | Lubricating oil composition for biodiesel engine and preparation method thereof | |
CN109679710B (en) | Hydraulic oil composition and preparation method thereof | |
CN109679712B (en) | Lubricating oil composition for high-speed diesel engine in railway and preparation method thereof | |
CN109679722B (en) | Composite calcium-based lubricating grease and preparation method thereof | |
CN109679730B (en) | Lubricating grease and preparation method thereof | |
CN109679718B (en) | Composite barium-based lubricating grease and preparation method thereof | |
CN109679716B (en) | Composite lithium-based lubricating grease and preparation method thereof | |
CN109679714B (en) | Composite sodium-based lubricating grease and preparation method thereof | |
CN109679721B (en) | Industrial lubricating oil composition and preparation method thereof | |
CN109679709B (en) | Universal gear lubricating oil composition and preparation method thereof | |
CN109679743B (en) | Fully synthetic industrial gear lubricating oil composition and preparation method thereof | |
CN109679717B (en) | Compressor lubricating oil composition and preparation method thereof | |
CN109679723B (en) | Turbine lubricating oil composition and preparation method thereof | |
CN109679737B (en) | Lubricating oil composition for marine medium-speed trunk piston engine and preparation method thereof | |
CN109679715B (en) | Automobile automatic transmission fluid composition and preparation method thereof | |
CN109679707B (en) | Gas engine lubricating oil composition and preparation method thereof | |
CN113512450B (en) | Two-stroke engine lubricating oil composition and preparation method thereof | |
WO2016039235A1 (en) | Lubricating oil additive and lubricating oil composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |