CN109679720B - Lubricating oil composition for diesel engine and preparation method thereof - Google Patents
Lubricating oil composition for diesel engine and preparation method thereof Download PDFInfo
- Publication number
- CN109679720B CN109679720B CN201710969292.3A CN201710969292A CN109679720B CN 109679720 B CN109679720 B CN 109679720B CN 201710969292 A CN201710969292 A CN 201710969292A CN 109679720 B CN109679720 B CN 109679720B
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- lubricating oil
- oil composition
- branched
- formula
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 46
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 46
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002199 base oil Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003599 detergent Substances 0.000 claims abstract description 23
- 229960002317 succinimide Drugs 0.000 claims abstract description 23
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims abstract 8
- -1 hydrocarbon radicals Chemical class 0.000 claims description 160
- 125000000217 alkyl group Chemical group 0.000 claims description 152
- 150000003254 radicals Chemical class 0.000 claims description 103
- 229910052739 hydrogen Inorganic materials 0.000 claims description 94
- 239000001257 hydrogen Substances 0.000 claims description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 51
- 125000003342 alkenyl group Chemical group 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 150000002431 hydrogen Chemical class 0.000 claims description 28
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 19
- 229920002367 Polyisobutene Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000012964 benzotriazole Substances 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 125000004434 sulfur atom Chemical group 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 239000004071 soot Substances 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 description 43
- 150000001565 benzotriazoles Chemical class 0.000 description 34
- 238000012360 testing method Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
- 239000008186 active pharmaceutical agent Substances 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000010710 diesel engine oil Substances 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012535 impurity Substances 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 238000004821 distillation Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- XPRULOZMJZDZEF-UHFFFAOYSA-N dibutoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCOP(S)(=S)OCCCC XPRULOZMJZDZEF-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000010705 motor oil Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 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
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 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
- LQSTWAYPHRSIDE-UHFFFAOYSA-N 6-ethyldecan-5-ylsulfanyl-dihydroxy-sulfanylidene-lambda5-phosphane Chemical compound C(CCC)C(C(CCCC)CC)SP(O)(O)=S LQSTWAYPHRSIDE-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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 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
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 108010011222 cyclo(Arg-Pro) Proteins 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry 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
- ZUNYMXPJGBXUCI-UHFFFAOYSA-N dioctoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(S)(=S)OCCCCCCCC ZUNYMXPJGBXUCI-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 238000011084 recovery Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003579 thiophosphoric acid derivatives Chemical class 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
- 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
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- 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
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- 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
- C10M169/04—Mixtures of base-materials and additives
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- 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
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- 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
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- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
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- C10N2040/25—Internal-combustion engines
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Abstract
The invention provides a lubricating oil composition for a diesel engine and a preparation method thereof. The lubricating oil composition for the diesel engine comprises benzotriazole derivatives, high-molecular succinimide ashless dispersants, mono-succinimide ashless dispersants, calcium sulfonate detergents, sulfurized calcium alkyl phenate detergents, alkylated diphenylamine type antioxidants, shielding phenol type antioxidants, dispersed OCP viscosity index improvers and lubricating oil base oil. The lubricating oil composition disclosed by the invention is low in ash content, has excellent high-temperature oxidation resistance, piston cleaning performance, soot dispersing performance and corrosion resistance, and can meet the requirements of high-performance diesel engine lubricating oil.
Description
Technical Field
The present invention relates to a lubricating oil composition, and particularly to a lubricating oil composition for a diesel engine.
Background
With the increasing strictness of environmental regulations, in order to reduce NOXAnd emission of harmful substances such as PM and CO, measures such as delayed injection, improvement of the position of an upper piston ring, arrangement of an EGR system and the like are widely adopted in the diesel engine. The measures reduce the exhaust emission, but greatly increase the soot content and soot particles in the diesel engine oil, and the accumulated soot aggravates the abrasion of key parts of engines such as engine piston rings, cylinder walls, valve systems and the like, thereby putting higher requirements on the abrasion resistance and soot dispersion performance of the oil.
The specifications of the diesel engine oil are developed from API CD, API CE, API CF-4, API CH-4 and API CI-4 to the current API CJ-4, and the specifications of the diesel engine oil have higher and higher requirements on various properties of oil products, particularly the anti-wear property of the oil products. In the API CD specification, there is no engine bench test for evaluating the antiwear properties of oil products; API CF-4 and API CH-4 require a Mack T-9 engine bench test to evaluate the wear of piston rings and cylinder liners in the presence of 2% soot; in the API CJ-4 specification, four engine bench tests of Mack T-12, RFWT, Cummins ISM and Cummins ISB respectively evaluate the wear of a piston ring and a cylinder sleeve in the presence of 6% soot, the wear of a roller driven part in the presence of 5% soot, the wear of a valve train in the presence of 5% soot and the wear of the valve train in the presence of 3.5% soot. Therefore, with the improvement of the quality grade of the diesel engine oil, the requirement on the anti-wear performance of the oil product is more and more strict.
Zinc dialkyldithiophosphate (ZDDP) is an antiwear, antioxidant, and anticorrosion multifunctional additive commonly used in internal combustion engine oils, but phosphorus-containing additives cause poisoning of catalysts in exhaust gas treatment devices, and thus phosphorus-containing additives are severely limited in oil specifications, and CJ-4 diesel engine oil specifications require a phosphorus content of less than 0.12% by mass, and it has been a continuing goal of those skilled in the art to seek more efficient ashless antiwear agents for use in diesel engine oils.
US 2736707(1956) proposes mannich base obtained by reacting dialkyl dithiophosphate with formaldehyde and amine as an oxidation corrosion inhibitor for internal combustion engine oil, which has extreme pressure properties. Its preparation process features that aqueous solution of formaldehyde, absolute alcohol and ether as solvent and hydrochloric acid as catalyst are used. The product needs to be subjected to the working procedures of solvent extraction, water washing, solvent recovery and the like, and the technical process is complex. The product is not subjected to stabilization treatment, so that the copper sheet is easy to discolor and cannot pass a copper sheet corrosion test. The process also produces large amounts of waste water containing formaldehyde and thiophosphoric acid derivatives.
Disclosure of Invention
The invention provides a lubricating oil composition for a diesel engine and a preparation method thereof.
Specifically, the present invention relates to the following aspects.
1. A lubricating oil composition for diesel engines comprises a benzotriazole derivative, a high-molecular succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, an alkylated diphenylamine type antioxidant, a shielded phenol type antioxidant, a dispersed OCP type viscosity index improver and lubricating oil base oil, wherein the benzotriazole derivative has a structure shown in a 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 radicalsThe 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), and 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 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 the group consisting of hydrogen, the group represented by the formula (I-1), the group represented by the formula (I-2) and C 1-4A 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 C1-20Hydrocarbyl, preferably independently selected from hydrogen and C1-20Straight or branched chain alkyl, more preferably each independently selected from hydrogen and C 1-6A linear or branched alkyl group,more preferably both are 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. The lubricating oil composition for diesel engines according to any of the preceding aspects, wherein the benzotriazole derivative is selected from the following specific compounds or a mixture of any two or more thereof:
3. a lubricating oil composition for diesel engines, comprising a benzotriazole derivative, a polymeric succinimide ashless dispersant, a monotetraimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkylphenate detergent, an alkylated diphenylamine-type antioxidant, a masked phenol-type antioxidant, a dispersed OCP-type viscosity index improver and a lubricating oil base oil, said benzotriazole derivative being 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, C10-25The group R' may also be hydrogen when it is a linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500); 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 X and Y radicals, equal to or different from each other, are each independently selected from the group consisting of an oxygen atom and a sulfur atom, preferably twoThe groups X are sulfur atoms, and the two 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 C1-20Hydrocarbyl, 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) 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 diesel engine lubricating oil composition according to any preceding aspect, wherein the benzotriazole derivative constitutes from 0.1% to 10% (preferably from 0.5% to 3%) of the total mass of the lubricating oil composition; the ashless macromolecular succinimide dispersant accounts for 1-15% (preferably 2-6%) of the total mass of the lubricating oil composition; the mono-succinimide ashless dispersant accounts for 1-15% (preferably 2-6%) of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% (preferably 1-4%) of the total mass of the lubricating oil composition; the sulfurized calcium alkyl phenate detergent accounts for 0.2 to 10 percent (preferably 1 to 4 percent) of the total mass of the lubricating oil composition; the alkylated diphenylamine type antioxidant accounts for 0.2-10% (preferably 1-3%) of the total mass of the lubricating oil composition; the shielding phenol type antioxidant accounts for 0.5-10% (preferably 1-2%) of the total mass of the lubricating oil composition; the dispersed OCP viscosity index improver accounts for 0.2-15% (preferably 0.5-10%) of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.
7. The lubricating oil composition for the diesel engine according to any one of the preceding aspects, wherein the number average molecular weight of a polyisobutylene part in the high molecular succinimide ashless dispersant is 1600-4000; the number average molecular weight of a polyisobutene part in the mono-succinimide ashless dispersant is 500-1500; the calcium sulfonate detergent is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate; the sulfurized calcium alkyl phenate detergent is selected from one or more of low-base-number sulfurized calcium alkyl phenate, medium-base-number sulfurized calcium alkyl phenate and high-base-number sulfurized calcium alkyl phenate; the alkyl of the alkylated diphenylamine type antioxidant is C1-12An alkyl group; the shielding phenol antioxidant is selected from monophenol antioxidant and/or bisphenol antioxidant; the nitrogen content of the dispersed OCP viscosity index improver is 0.05-5%; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oils.
The ashless polymeric succinimide dispersant may be selected from T161A and T161B manufactured by additive manufacturers of Kanz petrochemical Co., Ltd., LZL157 manufactured by Lubrizol additive Co., Ltd., LZ6418 and LZ6418B manufactured by Lubrizol Corporation, and the like.
The ashless mono-succinimide dispersant may be selected from T151A and T151B manufactured by additives works of Kansu Kasei Corporation, LZL151A manufactured by Lubrizol additives Co., Ltd., LZ894 manufactured by Lubrizol Corporation, and the like.
The calcium sulfonate detergent can be low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate. In order to better control the sulfated ash content of the oil product, the calcium sulfonate with the medium base number of (130-200) mgKOH/g is preferably selected. The calcium sulfonate detergent may be T105, T106, T104 from additive factories of Kanzhou petrochemical company, T102, T103, T107B from offshore additive factories, LZ6478, LZ58B, LZ75, LZ6446 from Lubrizol Corporation, C9353, C9330 from Infineum company, etc.
The sulfurized calcium alkyl phenate detergent can be low-base-number sulfurized calcium alkyl phenate, medium-base-number sulfurized calcium alkyl phenate and high-base-number sulfurized calcium alkyl phenate. In order to better control the sulfated ash of the oil product, the medium-base-value calcium alkyl sulfide with the base number of (130-200) mgKOH/g is preferred. The sulfurized calcium alkyl phenolate may be selected from S206 and T121 produced by Wuxi south petroleum additive Co., Ltd, LZL115A and LZL115B produced by Lubrizol additive Co., Ltd, LZ6499 and LZ6500 produced by Lubrizol Corporation, C9391 and C9394 produced by Infineum, etc. The alkyl group in the alkylated diphenylamine-type antioxidant is preferably located ortho or para to the amino group. The alkylated diphenylamine type antioxidant can be selected from T534 manufactured by Beijing Xingpo company, Irganox L57 manufactured by Ciba-Geigy Ltd company and the like.
The shielding phenol antioxidant can be selected from T501 produced by additive factories of Chinesota petrochemical company, Irganox L101, Irganox L109, Irganox L115, Irganox L1130, Irganox L134, Irganox L135 produced by Ciba-Geigy Ltd, and the like.
The nitrogen content of the dispersed OCP type viscosity index improver is 0.05-5%, and the dispersed OCP type viscosity index improver can be ECA8358, ECA8586 and the like of Exxon chemical company.
The lubricating oil base oil is preferably one or more of hydrogenated base oil, polyolefin synthetic base oil, alkylbenzene base oil and ester synthetic base oil.
8. A method for producing a lubricating oil composition for a diesel engine, characterized by mixing each additive in the lubricating oil composition according to any one of the above aspects with a lubricating base oil. The mixing temperature is preferably 40 ℃ to 90 ℃ and the mixing time is preferably 1 hour to 6 hours.
The lubricating oil composition has excellent high-temperature oxidation resistance, piston cleaning performance, soot dispersing performance and corrosion resistance, and can meet the requirements of high-performance diesel engine lubricating oil.
Technical effects
The benzotriazole derivative according to the present invention does not contain a metal element, is less likely 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). Which is not simultaneously possessed by the lubricating oil additives of the prior art.
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, it further exhibits excellent friction reducing properties while exhibiting excellent abrasion resistance. This is not the case with the prior art lubricating oil additives.
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 C1-30Straight or branched alkyl, C2-30Straight or branched alkenyl、C3-20Cycloalkyl radical, 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 having a carbon chain structure selected from the group consisting of-O-, -S-and-NR- (wherein the radical R is selected from the group consisting of H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) 1-4Straight-chain or branched alkyl, preferably selected from H and methyl). From the viewpoint of structural stability, it is preferable that when a plurality of them are present, 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 to be expressly noted here that, although said 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 referred to as 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, unless otherwise specified, any reference to Gel Permeation Chromatography (GPC) or measurement conditions of a GPC spectrum is: the instrument adopts a Waters 2695 type gel permeation chromatograph of Waters corporation 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 expressly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise generally recognized by those skilled in the art.
According to the invention, firstly, the benzotriazole derivative is shown as a general formula (I).
According to the invention, in the general formula (I), 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), 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-chain or branched alkenyl. Here, the C is defined as10-25Straight-chain or branched alkenyl groups, such as may be mentionedGo out 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) is 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), 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 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 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. Herein, asSaid C is2-5Examples 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, equal to or different from each other, are each independently selected from hydrogen, the radical represented by formula (I-1), the radical represented by formula (I-2), C1-6Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25Linear or branched alkenyl and polyisobutenyl 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 C1-4Straight 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 C 10-25Examples of the straight-chain alkyl group include n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n-tetracosyl, neododecyl, neotridecyl, neotetradecyl, neopentadecyl, neohexadecyl, neotetradecyl, and neotetradecylHeptaalkyl, neooctadecyl, neoeicosyl, neoheneicosyl, neotetracosyl and the like.
According to one embodiment of the invention, in the general formula (I), the group A 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 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 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), 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, by way of specific example, when n is 1, in formula (I), 3 of one of the radicals 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 of 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 the formula (I-1), one is a group represented by the formula (I-2), one is hydrogen, C1-4Straight or branched alkyl, C10-25Straight or branched alkyl, C10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.
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 R 1、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 the general 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 C 1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.
According to the invention, in the general formula (I-1), the radical 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, 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-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 independentlyIs 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, the C is defined as3-12Specific 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 the general formula (I-2), the radical 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 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-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 C3-12Examples of the straight-chain 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-heptylDecyl groups, and the like.
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, as the C10-25Straight or branched alkyl, such as C10-25Examples of the straight-chain alkyl group include n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n-tetracosyl, neododecyl, and neodecadecylTrialkyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, neotetracosyl group, etc.
According to one embodiment of the invention, in the general formula (I-B), 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 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-C10Homopolymerization of alpha-olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-deceneA polyolefin obtained by copolymerization of two or more kinds of (2).
According to a particular embodiment of the present 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 invention, in the general formula (I-B), n is 0, 1, 2 or 3, and may be, for example, 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 hydrocarbyl group having a number average molecular weight Mn of 300-3000.
According to a particular embodiment of the invention, in the formula (I-B), n +2 radicals A' are each otherThe same or different are independently selected from hydrogen and 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 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, 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 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 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-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-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), 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 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 C1-6More specific examples 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 using 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 cited. The mineral base oil includes, for example, 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 500-300 0, preferably 500-2500, most preferably 500-1500. Examples of the polyether include polymers produced 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 present invention, in the reaction step, for example, as the solvent, C may be mentioned2-10Aliphatic nitriles (e.g. acetonitrile, etc.), C6-20Aromatic hydrocarbons (e.g. benzene, toluene, xylene and cumene), C6-10Alkanes (e.g. n-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 dichloromethane, 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 comprise a certain amount of the diluent after being manufactured as described above, then the amount of the diluent added can be correspondingly reduced, and even used directly as an anti-wear agent without further addition of the diluent, as will be apparent to those skilled in the art.
Generally, 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 properties in examples and comparative examples were evaluated as follows.
(1) Evaluation of abrasion resistance
The lubricating oil compositions produced in the examples or comparative examples were subjected to a high-frequency back-and-forth friction test as test samples. The tester is HFRR tester manufactured by PCS company in England, and the test conditions are that the load is 500g, the frequency is 20Hz, the temperature is 100 ℃, and the test time is 60 min. And recording the diameter of the abrasion marks after the test is finished, wherein the smaller the diameter of the abrasion marks is, the better the abrasion resistance of the test sample is.
(2) Evaluation of copper sheet corrosion inhibition performance
The lubricating oil compositions produced in the examples or comparative examples were subjected to a copper sheet corrosion test as test samples with reference to the ASTM D130 standard method. And (3) immersing the polished copper sheet in the sample, heating to the test temperature of 121 ℃, keeping for 3 hours, taking out the copper sheet after the test is finished, and comparing the copper sheet with a corrosion standard color plate after washing to determine the corrosion grade.
(3) Thermal oxidation stability
The lubricating oil compositions produced in examples or comparative examples were used as test samples, and the thermal oxidation stability of the test samples was evaluated by a Pressurized Differential Scanning Calorimetry (PDSC) test, and expressed as the oxidation induction period (in min) of the test samples. The PDSC test was carried out at a temperature of 220 ℃ and a pressure of 0.5MPa with an oxygen flow rate of 100 mL/min.
(4) Evaluation of detergency
The cleaning properties of the lubricating oil compositions produced in examples or comparative examples were evaluated as test samples by the continuous coke-forming test, and are expressed in terms of the coke weight (in mg) of the test samples. The oil temperature of the test is 150 ℃, the plate temperature is 330 ℃, and the test time is 5 h. The lower the coke weight of the test coke-forming plate surface, the better the cleaning performance of the oil.
(5) Soot Dispersion Performance evaluation
The lubricating oil compositions manufactured in the examples or the comparative examples are used as test samples, oil products and 4% of carbon black are uniformly mixed through a high-speed emulsifying machine, the viscosity of the mixed oil products is measured, and the viscosity growth rate of the oil products is calculated to evaluate the soot dispersion performance of the oil products. The lower the viscosity growth rate, the better the soot dispersing properties of the oil.
Example 1
In a 250ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 23.01 g (86mmol) of octadecylamine, 20.27 g (250mmol) of a formaldehyde solution, 12.51 g (105mmol) of benzotriazole and 32.79 g (110mmol) of n-butyl 2-ethylhexyl dithiophosphoric acid were charged, rapidly stirred, and heated to 90 ℃ for reaction for 5 hours. And (3) after the reaction is finished, carrying out reduced pressure distillation to remove residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and carrying out column chromatography separation to obtain a final product, wherein the label is M-1.
Product characterization data are as follows:
1H NMR(300MHz，CDCl3)：δ0.88(9H)，1.03-1.72(40H)，2.12-3.93(10H)，4.20-4.54(2H)，5.18-6.17(4H)，7.18-8.08(4H)；
C38H69N4O2PS2calcd for C64.37, H9.81, N7.90, O4.51, P4.37, S9.04; measurement value: c64.57, H10.05, N7.54, O4.37, P4.42, S9.05.
Example 2
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 (3) after the reaction is finished, carrying out reduced pressure distillation to remove residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and carrying out column chromatography separation to obtain a final product, wherein the label is M-2.
Product characterization data were 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.
Example 3
Under the protection of nitrogen, 45 g of polyisobutene amine (with the number average molecular weight of about 600), 9 g (300mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 150mL of toluene are added into a 500mL four-neck flask provided with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, added with 24.4 g (100mmol) of di-n-butyl dithiophosphoric acid dropwise and reacted for 5 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-3.
Product characterization data were as follows:
1H NMR(300MHz，CDCl3)：δ0.86(9H)，0.97-1.91(86H)，3.46-4.87(6H)，5.23-6.35(2H)，7.19-8.08(4H)；
the measured value of the element content is as follows: c69.91, H11.23, N5.68, O3.35, P3.22, S6.61.
Example 4
50 g of polyisobutylene amide (number average molecular weight: about 600), 10.8 g (360mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 150mL of toluene were added to a 500mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, rapidly stirred, heated to 100 ℃ and 53.24 g (220mmol) of di-n-butyl dithiophosphoric acid was added dropwise and reacted for 5 hours at a constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-4.
Product characterization data were as follows:
1H NMR(300MHz，CDCl3)：δ0.86(9H)，0.97-1.75(101H)，2.54-4.03(16H)，4.26-5.93(6H)，7.19-8.08(4H)；
the measured value of the element content is as follows: c63.62, H10.55, N6.32, O4.95, P4.68, S9.88.
Comparative example 1
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 are 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.
Comparative example 2
In a 250mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 12.51 g (105mmol) of benzotriazole, 7.5 g (250mmol) of paraformaldehyde, 42.54 g (120mmol) of di-n-octyldithiophosphoric acid and 80mL of toluene were added, rapidly stirred, heated to 95 ℃ and reacted for 4 hours at a constant temperature. And (3) after the reaction is finished, carrying out reduced pressure distillation to remove residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and carrying out column chromatography separation to obtain a final product, wherein the label is D-2.
Product characterization data were as follows:
1H NMR(300MHz，CDCl3)：δ0.88(6H)，1.12-1.75(24H)，5.66(2H)，3.59-3.95(4H)，7.18-8.08(4H)；
C23H40N3O2PS2calcd for C56.88, H8.30, N8.65, O6.59, P6.38, S13.20; measurement value: c56.94, H8.35, N8.39, O6.64, P6.43, S13.25.
Examples I-1 to I-4 and comparative examples ID-1 to ID-5
Examples I-1 to I-4 and comparative examples ID-1 to ID-4, which were diesel engine oil compositions, were prepared according to the formulation compositions of Table 1. Comparative example ID-5 is a commercial API CJ-4 specification diesel engine oil.
List of additives used: t161, ashless dispersant of high molecular succinimide, stannless southern additive plant
T151, ashless mono-succinimide dispersant, tin-free southern Additor plant T105, medium base calcium sulfonate, Calif. petrochemical Co
T121, medium-basicity sulfurized calcium alkyl phenate, stanneless southern additive plant
T534 Diphenylamine antioxidant, Beijing Xinpu Fine chemical Co., Ltd
T512, screening phenol antioxidant, Beijing Xinpu Fine chemical Co., Ltd
ECA8358, Dispersion-type OCP viscosity index improver, Exxon chemical Co
T202, zinc butyl/isooctyl dithiophosphate, tin-free south additive plant
TABLE 1
The lubricating oil compositions of the above examples and the lubricating oil compositions of the comparative examples were evaluated for wear resistance, copper sheet corrosion inhibition, detergency, thermal oxidation stability and soot dispersion, respectively, and the results are shown in Table 2.
As can be seen from Table 2, the lubricating oil compositions of the present invention have excellent antiwear properties, corrosion inhibition properties, detergency, antioxidant properties and soot dispersion properties.
TABLE 2
Claims (21)
1. A lubricating oil composition for diesel engines comprises a benzotriazole derivative, a high-molecular succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, an alkylated diphenylamine type antioxidant, a shielding phenol type antioxidant, a dispersed OCP viscosity index improver and lubricating oil base oil, wherein the benzotriazole derivative has a structure shown in a 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 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), C1-25A 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 C1-20A hydrocarbyl group; radical R1、R2、R3、R4Are the same or different from each other and are each independently selected from hydrogen and C 1-20A hydrocarbon group ofStraight-chain or branched heteroalkyl means a radical obtained by interrupting the carbon chain structure of a straight-chain or branched alkyl radical by one or more hetero atom 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. The lubricating oil composition 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. The lubricating oil composition 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; r is1And R4Are each hydrogen, R2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen.
4. Lubricating oil composition according to claim 1, characterized in that in formula (I), the group R' is selected from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
5. Lubricating oil composition according to claim 1, characterized in that the number average molecular weight Mn is 500-2000.
6. Lubricating oil composition according to claim 1, characterized in that the number average molecular weight Mn is 500-1500.
7. Lubricating oil composition according to claim 1, characterized in that the benzotriazole derivative is selected from the following specific compounds or a mixture of any two or more thereof:
8. a lubricating oil composition for diesel engines, comprising a benzotriazole derivative, a polymeric succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, an alkylated diphenylamine type antioxidant, a masked phenol type antioxidant, a dispersed OCP type viscosity index improver and a lubricating oil base oil, said benzotriazole derivative being 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; 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, C 1-25A hydrocarbyl radical having a number average molecular weight Mn of 300-3000, with the proviso that at least two of the n +2 radicals A' represent hydrogen; when at least one of said groups A' is C10-25Straight 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、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.
9. The lubricating oil composition 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 C 2-5A 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 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 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. The lubricating oil composition 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, R 2And R3One of them is C1-10Straight or branched chain alkyl, the other being hydrogen.
11. Lubricating oil composition according to claim 8, characterized in that in formula (I), the group R' is selected from C1-20Hydrocarbyl and C3-20Linear or branched heteroalkyl.
12. Lubricating oil composition according to claim 8, characterized in that the number average molecular weight Mn is 500-2000.
13. Lubricating oil composition according to claim 8, characterised in that the number average molecular weight Mn is 500-1500.
14. The lubricating oil composition according to 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. Lubricating oil composition according to claim 8, wherein the reaction time of the reaction is from 0.5 to 6 hours and the reaction temperature of the reaction is from 60 to 120 ℃.
16. The lubricating oil composition according to claim 8, 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; 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: 1-10.
17. The lubricating oil composition according to claim 8, 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 1:0.6 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 1:0.6 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. Lubricating oil composition according to any one of claims 1 to 17, characterized in that the benzotriazole derivative constitutes from 0.1% to 10% of the total mass of the lubricating oil composition; the ashless macromolecular succinimide dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the mono-succinimide ashless dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% of the total mass of the lubricating oil composition; the sulfurized calcium alkyl phenate detergent accounts for 0.2-10% of the total mass of the lubricating oil composition; the alkylated diphenylamine antioxidant accounts for 0.2-10% of the total mass of the lubricating oil composition; the shielding phenol antioxidant accounts for 0.5-10% of the total mass of the lubricating oil composition; the dispersed OCP viscosity index improver accounts for 0.2-15% of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.
19. Lubricating oil composition according to any of claims 1 to 17, characterized in that the benzotriazole derivative constitutes 0.5 to 3% by mass of the total lubricating oil composition; the ashless macromolecular succinimide dispersant accounts for 2-6% of the total mass of the lubricating oil composition; the mono-succinimide ashless dispersant accounts for 2-6% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 1-4% of the total mass of the lubricating oil composition; the sulfurized calcium alkyl phenate detergent accounts for 1 to 4 percent of the total mass of the lubricating oil composition; the alkylated diphenylamine antioxidant accounts for 1-3% of the total mass of the lubricating oil composition; the shielding phenol type antioxidant accounts for 1-2% of the total mass of the lubricating oil composition; the dispersed OCP viscosity index improver accounts for 0.5-10% of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.
20. The lubricating oil composition according to any one of claims 1 to 17, wherein the number average molecular weight of the polyisobutylene moiety in the polymeric succinimide ashless dispersant is 1600 to 4000; the number average molecular weight of the polyisobutene part in the mono-succinimide ashless dispersant is 50 0 to 1500; the calcium sulfonate detergent is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate; the sulfurized calcium alkyl phenate detergent is selected from one or more of low-base-number sulfurized calcium alkyl phenate, medium-base-number sulfurized calcium alkyl phenate and high-base-number sulfurized calcium alkyl phenate; the alkyl of the alkylated diphenylamine antioxidant is C1-12An alkyl group; the shielding phenol type antioxidant is selected from monophenol type antioxidant and/or bisphenol type antioxidant; the nitrogen content of the dispersed OCP viscosity index improver is 0.05-5%; the lubricating oil base oil is selected from one or more of APII, II, III, IV and V base oils.
21. A method for preparing a lubricating oil composition as claimed in any one of claims 1 to 20, characterized in that the additives of the lubricating oil composition as claimed in any one of claims 1 to 20 are mixed with a lubricating base oil.
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