CN108034478A - 汽车齿轮油专用抗氧剂混合物 - Google Patents
汽车齿轮油专用抗氧剂混合物 Download PDFInfo
- Publication number
- CN108034478A CN108034478A CN201711344684.7A CN201711344684A CN108034478A CN 108034478 A CN108034478 A CN 108034478A CN 201711344684 A CN201711344684 A CN 201711344684A CN 108034478 A CN108034478 A CN 108034478A
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- China
- Prior art keywords
- oil
- antioxidant
- gear oil
- antioxidant mixture
- automobile gear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 68
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 57
- 239000012208 gear oil Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000004907 flux Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- -1 continue to stir 1 h Substances 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 239000002199 base oil Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 235000006708 antioxidants Nutrition 0.000 description 52
- 239000000047 product Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007866 anti-wear additive Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
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- 238000005461 lubrication Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- HLLOAHWFPRCYJY-UHFFFAOYSA-N 2h-benzotriazole;octadecan-1-amine Chemical group C1=CC=CC2=NNN=C21.CCCCCCCCCCCCCCCCCCN HLLOAHWFPRCYJY-UHFFFAOYSA-N 0.000 description 2
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical group NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 240000000203 Salix gracilistyla Species 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical class CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- MYRPZOHNKFKKPR-UHFFFAOYSA-N 2-butyl-4-octylphenol Chemical class CCCCCCCCC1=CC=C(O)C(CCCC)=C1 MYRPZOHNKFKKPR-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical class C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- VCQJSMBSGMLFKI-UHFFFAOYSA-N n-heptyl-n-phenylnaphthalen-1-amine Chemical group C=1C=CC2=CC=CC=C2C=1N(CCCCCCC)C1=CC=CC=C1 VCQJSMBSGMLFKI-UHFFFAOYSA-N 0.000 description 1
- ZLNMGXQGGUZIJL-UHFFFAOYSA-N n-octyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCC)C1=CC=CC=C1 ZLNMGXQGGUZIJL-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- NCEGDHPVRKYIJN-UHFFFAOYSA-N n-pentyl-n-phenylnaphthalen-1-amine Chemical group C=1C=CC2=CC=CC=C2C=1N(CCCCC)C1=CC=CC=C1 NCEGDHPVRKYIJN-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical class CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 231100000583 toxicological profile Toxicity 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/022—Well-defined aliphatic compounds saturated
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/044—Cyclic ethers having four or more ring atoms, e.g. furans, dioxolanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
- C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
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- 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
- 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
- C10M2215/064—Di- and triaryl amines
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- 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
- 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
- C10M2215/066—Arylene diamines
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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Abstract
本发明涉及一种汽车齿轮油专用抗氧剂混合物,其特征在于按质量分数包括以下成分:酚类抗氧剂3%~16%、溶剂32%~43%、稀释油29%~45%、胺类抗氧剂2%~18%,汽车齿轮油专用抗氧剂混合物的制备方法,包括以下步骤:酚类抗氧剂和溶剂按比例混合,40℃下搅拌1 h,加入一定量的稀释油继续搅拌0.5 h,缓慢加入一定量的胺类抗氧剂,继续搅拌1 h,制成抗氧剂混合物。其能配合基础油实现良好的抗氧化安定性能,是在现有齿轮油的基础上,进一步提高热氧化安定性,从而获得具有优异热氧化安定性的齿轮油,以适应现代齿轮传动系统。
Description
技术领域
本发明涉及一种汽车齿轮油专用抗氧剂混合物,属于齿轮油抗氧化安定性技术领域。
背景技术
随着车辆传动系硬件技术不断提高,长换油里程的呼声越来越高。目前汽车厂家逐步采用了商用车10万公里换油里程机械式变速器和中、后桥齿轮油,为了进一步延长换油里程,不仅要提高齿轮油抗磨性能,而且还要提高抗氧化等性能。
润滑油的氧化过程是一系列自由基反应过程,其具体过程已有诸多文献报道,其主要过程为润滑油分子在氧气作用下的一系列自由基反应:在高温和氧气作用下润滑油分子产生自由基,自由基与氧气或其他润滑油分子反应生成过氧化物,进而通过自由基链支化反应生成成分复杂的极性大分子物质,严重情况下极性大分子物质聚集并以油泥、积炭、漆膜等各种沉积物的形式沉积在部件表面。油品氧化的危害包括:1、油品黏度增长,导致流动性变差,润滑不良;2、产生酸性物质,长久积累对机械部件产生腐蚀;3、形成沉积物附着在部件表面,导致润滑油难以接触到须润滑的部件;4、油品性能衰减,缩短油品使用寿命。
研究发现,当齿轮油中加入抗氧剂时,可大大减缓氧化过程的发生。部分市场常见的车辆齿轮油使用多功能添加剂来提供一定的抗氧化作用。以二烷基二硫代磷酸锌类添加剂为例,它本身具有抗氧化的特性,同时可提供良好的极压抗磨保护,但在实际使用中,更侧重于极压抗磨作用。在日益苛刻的运行工况条件和延长换油里程的要求,多功能添加剂难以在抗氧化作用方面完全满足使用要求,而需额外加入专用抗氧剂来达到较好的热氧化安定性。
受阻酚类和胺类抗氧剂是润滑油中常用的典型抗氧剂。当在齿轮油中加入受阻酚类或胺类抗氧剂时,可在多功能添加剂的基础上进一步提高抗氧化性,大大减缓油品氧化过程及相关危害的产生,如100 ℃运动黏度和酸值上升等。此外,已发现受阻酚类和胺类抗氧剂在不同条件下的抗氧作用机理不同,如果搭配使用,可获得协同效应,抗氧效果优于单独使用一种抗氧剂,进一步提高润滑油的热氧化安定性和使用寿命。
专利CN106281576A报道了一种胺类抗氧剂的制备方法和润滑油组成,将芳胺、醛和胺类溶剂在0 ℃~150 ℃反应0.1 h~100 h,生成2、3、4个N-辛基苯基-1-萘胺分子与甲醛缩合的产物。本发明的制备方法简单、产物收率高。腐蚀和氧化安定性试验结果表明本发明的胺类抗氧剂和润滑油组合物具有优异的高温抗氧化性,能够有效地抑制油品的黏度增加和酸值增长,减少氧化沉积物的产生。但是生产工艺复杂,不易实现,需要N2保护状态下进行电磁搅拌,并且化合物(Ⅳ)的反应收率低。
专利CN104893788A报道了一种应用于齿轮油的高温抗氧剂,该抗氧剂以对特辛基酚、正己烷、二氯化硫、烯基丁二酸酚、苯、硫代双对特辛基苯酚苯和水合醋酸铜为原料,合成复合型抗氧剂2,2’一硫代双对特辛基苯酚烯基丁二酸铜。通过L-60-1热氧化安定性试验、SAE J2360橡胶相容性试验、高温积炭模拟试验和极压性能试验,证明该抗氧剂提高了齿轮油的抗氧化能力,有效降低车辆积炭形成,延长了换油周期,提高了经济效益。但是原料成本较高,制备工艺复杂,毒性较大,有害副产物较多,不符合当前成本和环保的实际要求。
对于胺类抗氧剂,例如N-苯基-α-萘胺、辛基苯基-α-萘基胺、二甲苯基萘胺、十二烷基苯基萘基胺、N叔-叔戊基-苯基-α-萘胺、N-庚基苯基-α-萘胺、对叔丁基苯基和对十二烷基苯基 -α-萘基胺和Np-(1:3:3:5:5-六甲基己基)-苯基-α-萘胺等抗氧剂,虽然α-异构体和β-异构体都是有效的抗氧剂,但是只有苯基-α-萘胺及其衍生物目前正在使用,因为β-萘胺中间体是已知的致癌物质,而且这类抗氧剂价格比较高,所以主要用于特别苛刻的高温条件,其他物质则是β-异构体或带有不同形式烷基取代的萘胺结构。
发明内容
本发明的目的在于提供了一种汽车齿轮油专用抗氧剂混合物,并能配合基础油实现良好的抗氧化安定性能,是在现有齿轮油的基础上,进一步提高热氧化安定性,从而获得具有优异热氧化安定性的齿轮油,以适应现代齿轮传动系统。
本发明的技术方案是这样实现的:汽车齿轮油专用抗氧剂混合物,其特征在于按质量分数包括以下成分:
酚类抗氧剂 3 %~16 %
溶剂 32 %~43 %
稀释油 29 %~45 %
胺类抗氧剂 2 %~18 %
其中酚类抗氧剂为2,6-二特丁基苯酚和2,6-二叔丁基对甲酚中一种或两种;
溶剂为N,N-二甲基甲酰胺、正庚烷和正己烷中一种;
稀释油为二氯甲烷、四氢呋喃、甲苯、乙醚和氯仿中一种;
胺类抗氧剂为二烷基二苯胺和N,N'-二苯基-对苯二胺中一种或两种;
汽车齿轮油专用抗氧剂混合物的制备方法,包括以下步骤:
酚类抗氧剂和溶剂按比例混合,40 ℃下搅拌1 h,加入一定量的稀释油继续搅拌0.5h,缓慢加入一定量的胺类抗氧剂,继续搅拌1 h,制成抗氧剂混合物。
本发明的积极效果是在提高抗氧化性能基础上,将酚类抗氧剂能够有效控制油泥形成能力以及胺类抗氧剂能够控制黏度和酸值变化能力结合起来,表现出良好的抗氧化性能和耐高温性能,解决了单一抗氧剂使用温度低或者易产生沉淀的问题,并且能够配合基础油实现良好的抗氧化安定性能,提高了齿轮油的使用寿命,有利于延长换油里程。本发明选用胺类抗氧剂之一为二烷基二苯胺,二苯胺本身是有效的抗氧剂,但其以烷基化形式在润滑油中应用更为广泛,烷基化改善了二苯胺的极性以及氧化消耗后相应产物的油溶性,增加了分子量来降低挥发性,这些均有利于抗氧剂在油品中发挥有效作用。另外与二苯胺相比,烷基化二苯胺显著改善了毒理学特性和环境影响。本发明选用胺类抗氧剂之二为N,N'-二苯基-对苯二胺,该物质属于芳香二胺,苯二胺和邻苯二胺均属于同一类胺类抗氧剂。N,N’-二苯基对苯二胺是这类物质中比较有效抗氧剂,其中苯基可以被甲基、乙基或甲氧基等基团取代,具有良好的抗氧化性。如果胺类抗氧剂质量分数低于2 %,则达不到预期的抗氧效果,高于18 %,造成成本增加,还需要考虑与极压抗磨剂的协同作用。
对于酚类抗氧剂,一类酚类抗氧剂是在受阻酚基础上进行更复杂的衍生包括各种烷基化、酯化等,例如2,6-二叔丁基-4-乙基苯酚、2,6-二叔丁基-4-正丁基苯酚、2,6-二叔丁基-4-辛基苯酚、4-羟甲基-2,6-二叔丁基苯酚、正十八烷基-β(3,5-二叔丁基-4-羟基苯基)丙酸酯和2,6-甲基-4-十二烷基苯酚等酚类抗氧剂,优点是保持原有的抗氧性能,同时降低挥发性,提高在油品中的溶解性,所以在高温或长久使用过程中抗氧剂在油品中的保持性更好(主要用于发动机油),另外这些衍生物部分结构在常温下呈液态,且与油品其他成分相容性更好,方便操作。缺点是由于引入的烷基或其他衍生结构不存在抗氧效果,受阻酚基团的质量分数稍低,生产工艺复杂,成本高。另一类酚类抗氧剂是在分子内引入多个受阻酚结构,例如2,2'-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2'-亚甲基双(4-乙基-6-叔丁基苯酚)、4,4’-双(2,6-二特丁基苯酚)、4,4’-亚甲基双(2,6-二特丁基苯酚)、三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、2,2'-氧杂二酰基双(乙基-3-(3,5-二叔丁基-4-羟基苯基))丙酸酯和1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯等酚类抗氧剂,这类酚类抗氧剂每个分子中的有效抗氧基团增多,抗氧化能力更强。缺点是分子较大,以固体为主,溶解性和相容性在一定程度上有些影响,且生产上同样是以二叔丁基苯酚为基础,复杂度稍高。
本发明选用2,6-二特丁基苯酚和2,6-二叔丁基对甲酚,这两个受阻酚类抗氧剂结构简单,抗氧效果好,是众多领域最常用的受阻酚类抗氧剂,而且这两个物质是合成一些更复杂酚类抗氧剂的原材料,所以生产工艺简单,经济性高。如果胺类抗氧剂质量分数低于3%,则达不到预期的抗氧效果,高于16 %,造成成本增加。
具体实施方式
为使本发明实施例的目的和技术方案更加清楚,下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
本技术领域技术人员可以理解,除非另外定义,这里使用的所有术语(包括技术术语和科学术语)具有与本发明所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是,诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中意义一致的意义,并且除非像这里一样定义,不会用理想化或过于正式的含义来解释。
实施例1
添加专用抗氧剂混合物的齿轮油按质量分数组成:
二类基础油为500N,其用量为95.3%;
极压抗磨剂为硫代磷酸酯胺盐,其用量为2%;
金属腐蚀抑制剂为苯三唑脂肪胺衍生物,其用量为0.5%;
抗氧剂为二烷基二苯胺、2,6-二特丁基苯酚和2,6-二叔丁基对甲酚,比例1:1:1,其用量范围为1.0 %;
清净剂为环烷酸钙,其用量范围为0.2 %;
分散剂为丁二酰亚胺,其用量范围为0.5 %;
降凝剂为聚甲基丙烯酸酯KS 300,其用量范围为0.25 %;
抗泡剂为甲苯基硅油,其用量范围为0.25 %。
按质量分数将2,6-二特丁基苯酚、2,6-二叔丁基对甲酚按1:1比例形成的混合物10 %与40 %的正己烷混合,40 ℃下搅拌1 h,加入40 %的二氯乙烷继续搅拌0.5 h,缓慢加入10 %的二烷基二苯胺,继续搅拌1 h,制成抗氧剂混合物。
在带搅拌器的反应釜中加入一定量的二氯乙烷,然后加入环烷酸钙,在60 ℃~70℃下搅拌2 h~4 h至完全溶解,降温到30 ℃~50 ℃,加入硫代磷酸酯胺盐、抗氧剂混合物和苯三唑脂肪胺衍生物,在30 ℃~50 ℃下搅拌4 h~6 h至全部溶解,得到复合添加剂。
在反应釜中加入所需量的基础油,搅拌升温到50 ℃~60 ℃,将已稀释好的甲苯基硅油和聚甲基丙烯酸酯KS 300分别加入基础油中,在50 ℃~85℃下搅拌2 h~4 h,最后加入制备好的复合添加剂,充分搅拌,得到成品油。
实施例2
添加专用抗氧剂混合物的齿轮油按质量分数组成:
二类基础油为500N,其用量为92.25 %;
极压抗磨剂为硫代磷酸酯胺盐,其用量为4 %;
金属腐蚀抑制剂为苯三唑十八胺盐T406,其用量为1 %;
抗氧剂为N,N'-二苯基-对苯二胺和2,6-二特丁基苯酚,比例为1:1,其用量范围为0.5%;
清净剂为石油磺酸钙,其用量范围为1 %;
分散剂为丁二酰亚胺,其用量范围为0.5 %;
降凝剂为聚α-烯烃,其用量范围为0.5 %;
抗泡剂为聚甲基硅油,其用量范围为0.25 %。
按质量分数将2,6-二特丁基苯酚10 %与40 %的正己烷混合,40 ℃下搅拌1 h,加入40 %的四氢呋喃继续搅拌0.5 h,缓慢加入10 %的N,N'-二苯基-对苯二胺,继续搅拌1 h,制成抗氧剂混合物。
在带搅拌器的反应釜中加入一定量的四氢呋喃,先加入石油磺酸钙,在60 ℃~70℃下搅拌2 h~4 h至完全溶解,降温到30 ℃~50 ℃,加入硫代磷酸酯胺盐、抗氧剂混合物和苯三唑十八胺盐T406衍生物,在30 ℃~50 ℃下搅拌4 h~6 h至全部溶解,得到复合添加剂。
在反应釜中加入所需量的基础油,搅拌升温到50 ℃~60 ℃,将已稀释好的聚甲基硅油和聚α-烯烃分别加入基础油中,在50 ℃~85 ℃下搅拌2 h~4 h,最后加入制备好的复合添加剂,充分搅拌,得到成品油。
实施例3
添加专用抗氧剂混合物的齿轮油按质量分数组成:
二类基础油为500N,其用量为92.4 %;
极压抗磨剂为硫代磷酸酯胺盐,其用量为4 %;
金属腐蚀抑制剂为N,N'-二亚水杨-1,2丙二胺,其用量为1 %;
抗氧剂为N,N'-二苯基-对苯二胺和2,6-二叔丁基对甲酚,比例1:1,其用量范围为0.5%;
清净剂为石油磺酸镁,其用量范围为0.5 %;
分散剂为丁二酰亚胺,其用量范围为1 %;
降凝剂为聚α-烯烃,其用量范围为0.3 %;
抗泡剂为二甲基硅油,其用量范围为0.3 %。
按质量分数将2,6-二叔丁基对甲酚的10 %与40 %的正己烷混合,40 ℃下搅拌1h,加入40 %的二氯乙烷继续搅拌0.5 h,缓慢加入10 %的N,N'-二苯基-对苯二胺,继续搅拌1 h,制成抗氧剂混合物。
在带搅拌器的反应釜中加入一定量的二氯乙烷,先加入石油磺酸镁,在60 ℃~70℃下搅拌2 h~4 h至完全溶解,降温到30 ℃~50 ℃,加入硫代磷酸酯胺盐、抗氧剂混合物和N,N'-二亚水杨-1,2丙二胺衍生物,在30 ℃~50 ℃下搅拌4 h~6 h至全部溶解,得到复合添加剂。
在反应釜中加入所需量的基础油,搅拌升温到50 ℃~60 ℃,将已稀释好的二甲基硅油和聚α-烯烃分别加入基础油中,在50 ℃~85 ℃下搅拌2 h~4 h,最后加入制备好的复合添加剂,充分搅拌,得到成品油。
试验例
试验结果表明,实施例1中齿轮油闪点(开口)和表观黏度数值优于市售油。
按照SH/T 0755-2005《手动变速箱油和后桥用油的热氧化安定性评定法(L-60-1法)》,对本实施例1中齿轮油和市售齿轮油进行L-60-1热氧化安定性试验,50 h试验均能通过标准要求。为了强化试验条件,进行200 h的L-60-1热氧化安定性试验,试验结果如表2所示,实施例1中齿轮油的100 ℃运动黏度增长通过了加强版的L-60-1试验,市售油1和市售油2的100 ℃运动黏度增长均未通过加强版的L-60-1试验,实施例1中齿轮油的热氧化安定性较好。
试验结果表明,实施例1中齿轮油的铜片腐蚀结果较好,试验后100 ℃运动黏度变化率和铜含量更低。
以上仅为本发明的实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些均属于本发明的保护范围。
Claims (6)
1.汽车齿轮油专用抗氧剂混合物,其特征在于按质量分数包括以下成分:
酚类抗氧剂 3 %~16 %
溶剂 32 %~43 %
稀释油 29 %~45 %
胺类抗氧剂 2 %~18 %。
2.根据权利要求1所述的汽车齿轮油专用抗氧剂混合物,其特征在于所述的酚类抗氧剂为2,6-二特丁基苯酚和2,6-二叔丁基对甲酚中一种或两种。
3.根据权利要求1所述的汽车齿轮油专用抗氧剂混合物,其特征在于所述的溶剂为N,N-二甲基甲酰胺、正庚烷和正己烷中一种。
4.根据权利要求1所述的汽车齿轮油专用抗氧剂混合物,其特征在于所述的稀释油为二氯甲烷、四氢呋喃、甲苯、乙醚和氯仿中一种。
5.根据权利要求1所述的汽车齿轮油专用抗氧剂混合物,其特征在于所述的胺类抗氧剂为二烷基二苯胺和N,N'-二苯基-对苯二胺中一种或两种。
6.根据权利要求1所述的汽车齿轮油专用抗氧剂混合物,其特征在于所述的抗氧剂混合物的制备步骤如下:
酚类抗氧剂和溶剂按比例混合,40 ℃下搅拌1 h,加入一定量的稀释油继续搅拌0.5h,缓慢加入一定量的胺类抗氧剂,继续搅拌1 h,制成抗氧剂混合物。
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