CN1675341A - 包含铅腐蚀抑制剂的发动机油 - Google Patents
包含铅腐蚀抑制剂的发动机油 Download PDFInfo
- Publication number
- CN1675341A CN1675341A CNA038188643A CN03818864A CN1675341A CN 1675341 A CN1675341 A CN 1675341A CN A038188643 A CNA038188643 A CN A038188643A CN 03818864 A CN03818864 A CN 03818864A CN 1675341 A CN1675341 A CN 1675341A
- Authority
- CN
- China
- Prior art keywords
- triazole
- aminomethyl
- composition
- additive
- engine oil
- 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.)
- Pending
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- 239000010705 motor oil Substances 0.000 title claims abstract description 39
- 239000003112 inhibitor Substances 0.000 title description 2
- 239000000654 additive Substances 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- -1 (2-ethylhexyl) aminomethyl Chemical group 0.000 claims description 80
- 150000003852 triazoles Chemical class 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 44
- 239000003921 oil Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000007866 anti-wear additive Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229940038384 octadecane Drugs 0.000 claims description 3
- JZSFJRODQAKRNT-UHFFFAOYSA-N 6-methyl-n-(6-methylheptyl)-n-(1,2,4-triazol-1-ylmethyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CN1C=NC=N1 JZSFJRODQAKRNT-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 241000283984 Rodentia Species 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims 1
- 239000006078 metal deactivator Substances 0.000 abstract description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract 2
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 239000008158 vegetable oil Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 21
- 150000002148 esters Chemical class 0.000 description 19
- 239000011133 lead Substances 0.000 description 18
- 229960003742 phenol Drugs 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 6
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 6
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000010710 diesel engine oil Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- AVBBHCMDRGQBNW-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-(1,2,4-triazol-1-ylmethyl)hexan-1-amine Chemical compound CCCCC(CC)CN(CC(CC)CCCC)CN1C=NC=N1 AVBBHCMDRGQBNW-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical class CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 3
- RJDVGKCBHFINOK-UHFFFAOYSA-N tris(2-methylphenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RJDVGKCBHFINOK-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MSGFMKMFGGXSTO-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC Chemical compound C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC MSGFMKMFGGXSTO-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001356 alkyl thiols Chemical class 0.000 description 2
- 125000005466 alkylenyl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
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- 150000002632 lipids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000008427 organic disulfides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 229920000098 polyolefin Polymers 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical class CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 1
- ZIJHTQPOUJBOHK-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl)methylphosphonic acid Chemical class CC1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZIJHTQPOUJBOHK-UHFFFAOYSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10M135/02—Sulfurised compounds
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- C10M2219/066—Thiocarbamic type compounds
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- C10M2219/068—Thiocarbamate metal salts
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- C10M2223/045—Metal containing thio derivatives
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- C10M2223/047—Thioderivatives not containing metallic elements
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- C10M2227/09—Complexes with metals
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Abstract
包含某些1，2，4－三唑金属钝化剂的调配发动机油对于铅制发动机零件如轴承来说尤其具有非侵蚀性。包含某些1，2，4－三唑化合物使得诸如含硫添加剂的腐蚀性添加剂和由植物油衍生的摩擦改性剂可以一起使用，同时可满足ASTMD4485的要求。
Description
本发明涉及对于铅制品具有非侵蚀性的发动机油(发动机液)组合物。
美国专利说明书4,734,209公开了用于官能液的金属钝化剂。
美国专利说明书4,491,527公开了可用于在润滑剂中抑制铅漆沉积的组合物。
发动机油的技术规范在性能要求方面正在变得更加严格，并且为了满足这些新的技术规范，正在研制新的配方。在ASTM D 4485中对发动机油技术规范进行了定义。
正在研制中的新的发动机油配方包含某些添加剂化学品。这些添加剂化学品中有许多对于铅来说是有腐蚀性的。对于配方设计师来说，通过使用某些有益的添加剂来满足现今的发动机油技术规范同时还满足对于铅制品腐蚀性的技术要求是很困难的。
从1994年起，已经要求所有的柴油机油要满足ASTM D 4485中定义的、和根据ASTM D 5968(在125℃下运行)或ASTM D 6594(在135℃运行)所测定的对于铅制品腐蚀的规格标准。用于发动机油性能的ASTM D 4485标准规范表明，用ASTM D 5968测定时，对于API类CF-4和CG-4来说，铅腐蚀的最高容许量为60ppm，而通过ASTM D 6594测定时，对于类别CH-4来说，铅腐蚀的最高容许量为120ppm。
例如，调配发动机油中导致发生铅腐蚀的某些组分包含某些洗涤剂，耐磨添加剂，摩擦改性剂和抗氧化剂。许多这种希望的添加剂化学品均由于会导致发动机油配方不能满足铅腐蚀限制方面的工业技术规范而无法得到使用。
例如，对于铅具有腐蚀性，换句话说没有资格用于发动机油中的希望的添加剂化学品包括含硫添加剂和某些由植物油衍生的摩擦改性剂。
令人惊奇的是，已经发现，包含某些1，2，4-三唑金属钝化剂的调配发动机油对于铅制品，例如铅制发动机零件如轴承尤其具有非侵蚀性。根据本发明的发动机油满足ASTM D 4485中定义的柴油机润滑剂技术规范的防腐性能要求。
在其他类型的润滑剂如涡轮油和液压油中，铅腐蚀的问题通常不是一个问题。
本发明的发动机油是柴油机油和通用油。通用油既包含柴油机油，又包含客车油。发动机油用于内燃机中，例如装有如奥图、狄塞耳、双冲程、旺克尔或轨道型发动机的机动车辆中。
具体地说，本发明涉及对于铅制品不具有侵蚀性的发动机油组合物，该组合物包含：
(a)基液，
(b)至少一种式(I)的化合物，
(c)至少一种对于铅制品有腐蚀性的油添加剂，所述油添加剂选自抗氧化剂，耐磨添加剂，分散剂，洗涤剂，消泡添加剂，粘度指数改进剂，铜钝化剂，防锈剂，降凝剂，破乳剂和摩擦改性剂，
其中：
R1和R2相同或不同，是C1-C20烷基，C3-C20烯基，C5-C12环烷基，C7-C13芳烷基，或C6-C10芳基，或R1和R2与和它们各自连接的氮原子一起可以形成5-、6-或7-元杂环残基，或R1和R2是下式的基团：
R3X[(-R4-)O]n(-R4)-
其中：
X是O、S或N，
R3是氢或C1-C20烷基，
R4是C1-C12亚烷基，
n是0或1-6的整数，
或R1和R2中的一个是下式(II)的基团：
或R2是式(II)的基团而R1是下式的基团：
-[R4]n-N(R5)-A-[N(R5)2]m
其中：
m是0或1，且当m是0时，A是式(II)的基团，当m是1时，A是亚烷基或C6-C10亚芳基，R5是式(II)的基团，并且，
当在没有组分(b)的情况下，该发动机油组合物在根据ASTM D6594试验测定时铅超过约100ppm。
R4是，例如，C1-C6亚烷基，例如，C2-C3亚烷基。
数字n是例如，0，1，2，3，4，5或6。
烷基是直链或支链的，并且是例如，甲基，乙基，正丙基，异丙基，正丁基，仲丁基，正戊基，正己基，正庚基，正辛基，2-乙基己基，正壬基，正癸基，正十二烷基，正十四烷基，正十六烷基，正十八烷基或正二十烷基。
烯基是直链或支链的，并且是例如，丙-2-烯基，丁-2-烯基，2-甲基-丙-2-烯基，戊-2-烯基，己-2，4-二烯基，癸-10-烯基或二十-2-烯基。
环烷基是，例如，环戊基，环己基，环辛基，环癸基，金刚烷基或环十二烷基。
芳烷基是，例如，苄基，2-苯乙基，二苯甲基或萘甲基。
芳基是，例如，苯基或萘基。
当R1和R2和与它们连接的氮原子一起形成杂环基，所述杂环基是，例如，吗啉，吡咯烷，哌啶或全氢氮杂环。
亚烷基包括，例如，亚甲基，亚乙基，1：2-或1：3-亚丙基，1：4-亚丁基，1：6-亚己基，1：8-亚辛基，1：10-亚癸基，和1：12-亚十二烷基。
亚芳基包括，例如，亚苯基和亚萘基。
本发明式(I)的具体化合物包括：
1-(或4)-(二甲基氨甲基)三唑；
1-(或4)-(二乙基氨甲基)三唑；
1-(或4)-(二异丙基氨甲基)三唑；
1-(或4)-(二正丁基氨甲基)三唑；
1-(或4)-(二正己基氨甲基)三唑；
1-(或4)-(二异辛基氨甲基)三唑；
1-(或4)-(二(2-乙基己基)氨甲基)三唑；
1-(或4)-(二正辛基氨甲基)三唑；
1-(或4)-(二正癸基氨甲基)三唑；
1-(或4)-(二正十二烷基氨甲基)三唑；
1-(或4)-(二正十八烷基氨甲基)三唑；
1-(或4)-(二正二十烷基氨甲基)三唑；
1-[或4)-[二(丙-2′-烯基)氨甲基]三唑；
1-[或4)-[二(丁-2′-烯基)氨甲基]三唑；
1-[或4)-[二(二十-2′-烯基)氨甲基]三唑；
1-(或4)-(二环己基氨甲基)三唑；
1-(或4)-(二苄基氨甲基)三唑；
1-(或4)-(二苯基氨甲基)三唑；
1-(或4)-(4′-吗啉甲基)三唑；
1-(或4)-(1’-吡咯烷甲基)三唑；
1-(或4)-(1’-哌啶甲基)三唑；
1-(或4)-(1’-全氢氮杂甲基)三唑；
1-(或4)-(2′，2″-二羟乙基)氨甲基]三唑；
1-(或4)-(二丁氧基丙基氨甲基)三唑；
1-(或4)-(二丁硫基丙基氨甲基)三唑；
1-(或4)-(二丁氨基丙基氨甲基)三唑；
N，N-二(1-或4-三唑基甲基)月桂胺；
N，N-二(1-或4-三唑基甲基)油胺；
N，N-二(1-或4-三唑基甲基)乙醇胺和
N，N，N′，N′-四-(1-或4-三唑基甲基)乙二胺。
式(I)的典型化合物是，例如，1-(二异辛基氨甲基)三唑，即，1-(二异辛基氨甲基)-1，2，4-三唑，或1-(二(2-乙基己基)氨甲基)-1，2，4-三唑。
本发明的式(I)化合物是通过已知方法制备的，例如，美国专利说明书4,734,209中公开的方法，其内容在此引入作为参考。
根据本发明的基液使用矿物油基液体(API族I，II和III)，聚-α-烯烃-PAO(API族IV)，酯(API族V)，其他的合成液，动物或植物性来源的天然油，和其混合物。基液具有用于发动机油场合的适当的粘度。
本发明式(I)化合物的使用浓度为，以调配发动机油的重量计约0.01-约1.0重量％。例如，式(I)化合物的存在量为约0.02-约0.5重量％；例如，为约0.03-约0.3重量％；例如，为约0.01-约0.5重量％或约0.01-约0.3重量％；例如，为约0.02-约1.0重量％或约0.02-约0.3重量％；例如，为约0.03-约1.0重量％或约0.03-约0.5重量％。
适当的组分(c)的抗氧化剂选自：
1)烷基化的一元酚，例如2，6-二叔丁基-4-甲基苯酚，2-叔丁基-4，6-二甲基苯酚，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-异丁基苯酚，2，6-二环戊基-4-甲基苯酚，2-(α-甲基环己基)-4，6-二甲基苯酚，2，6-二-十八碳烷基-4-甲基苯酚，2，4，6-三-环己基苯酚，2，6-二叔丁基-4-甲氧基甲基苯酚，线性或在侧链上带叉链的壬基酚类诸如2，6-二-壬基-4-甲基苯酚，2，4-二甲基-6-(1′-甲基十一碳烷-1′-基)苯酚，2，4-二甲基-6-(1′-甲基十七碳烷-1′-基)苯酚，2，4-二甲基-6-(1′-甲基十三碳烷-1′-基)苯酚以及它们的混合物。
2)烷基硫甲基酚类，例如2，4-二辛基硫甲基-6-叔丁基苯酚，2，4-二辛基硫甲基-6-甲基苯酚，2，4-二辛基硫甲基-6-乙基苯酚，2，6-二-十二碳烷基硫甲基-4-壬基苯酚。
3)氢醌类和烷基化的氢醌类，例如2，6-二-叔丁基-4-甲氧基苯酚，2，5-二-叔丁基氢醌，2，5-二-叔戊基氢醌，2，6-二苯基-4-十八碳烷氧基苯酚，2，6-二叔丁基氢醌，2，5-二叔丁基-4-羟基苯甲醚，3，5-二叔丁基-4-羟基苯甲醚，硬脂酸3，5-二叔丁基-4-羟基苯基酯，己二酸双(3，5-二叔丁基-4-羟基苯基)酯。
4)生育酚类，例如α-生育酚，β-生育酚，γ-生育酚，δ-生育酚和它们的混合物(维生素E)。
5)羟基化的硫代二苯醚类，例如2，2′-硫代双(6-叔丁基-4-甲基苯酚)，2，2′-硫代双(4-辛基苯酚)，4，4′-硫代双(6-叔丁基-3-甲基苯酚)，4，4′-硫代双(6-叔丁基-2-甲基苯酚)，4，4′-硫代双(3，6-二-仲戊基苯酚)，4，4′-双(2，6-二甲基-4-羟基苯基)-二硫化物。
6)亚烷基双酚类，例如2，2′-亚甲基双(6-叔丁基-4-甲基苯酚)，2，2′-亚甲基双(6-叔丁基-4-乙基苯酚)，2，2′-亚甲基双(4-甲基-6-(α-甲基环己基)苯酚)，2，2′-亚甲基双(4-甲基-6-环己基苯酚)，2，2′-亚甲基双(6-壬基-4-甲基苯酚)，2，2′-亚甲基双(4，6-二叔丁基苯酚)，2，2′-亚乙基双(4，6-二叔丁基苯酚)，2，2′-亚乙基双(6-叔丁基-4-异丁基苯酚)，2，2′-亚甲基双(6-(α-甲基苄基)-4-壬基苯酚)，2，2′-亚甲基双(6-(α，α-二甲基苄基)-4-壬基苯酚)，4，4′-亚甲基双(2，6-二叔丁基苯酚)，4，4′-亚甲基双(6-叔丁基-2-甲基苯酚)，1，1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷，2，6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚，1，1，3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷，1，1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二碳烷基巯基丁烷，乙二醇双(3，3-双(3′-叔丁基-4′-羟基苯基)丁酸酯)，双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯，对苯二甲酸双(2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基)酯，1，1-双(3，5-二甲基-2-羟基苯基)丁烷，2，2-双-(3，5-二叔丁基-4-羟基苯基)丙烷，2，2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二碳烷基巯基丁烷，1，1，5，5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
7)O-、N-、和S-苄基化合物，例如3，5，3′，5′-四叔丁基-4，4′-二羟基二苄基醚，十八碳烷基-4-羟基-3，5-二甲基苄基巯基乙酸酯，十三碳烷基-4-羟基-3，5-二-叔丁基苄基巯基乙酸酯，三(3，5-二叔丁基-4-羟基苄基)胺，双(4-叔丁基-3-羟基-2，6-二甲基苄基)二硫代对苯二甲酸酯，双(3，5-二叔丁基-4-羟基苄基)硫化物，异辛基-3，5-二叔丁基-4-羟基苄基巯基乙酸酯。
8)羟苄基化的丙二酸酯类，2，2-双(3，5-二叔丁基-2-羟苄基)丙二酸二-十八碳烷基酯，2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二-十八碳烷基酯，2，2-双(3，5-二叔丁基-4-羟基苄基)丙二酸二-十二碳烷基巯基乙基酯，2，2-双(3，5-二叔丁基-4-羟基苄基)丙二酸双(4-(1，1，3，3-四甲基丁基)苯基)酯。
9)芳香羟苄基化合物，例如1，3，5-三(3，5-二叔丁基-4-羟基苄基)-2，4，6-三甲基苯，1，4-双(3，5-二叔丁基-4-羟基苄基)-2，3，5，6-四甲基苯或2，4，6-三(3，5-二叔丁基-4-羟基苄基)苯酚。
10)三嗪类化合物，例如2，4-双(辛基巯基)-6-(3，5-二叔丁基-4-羟基苯胺基)-1，3，5-三嗪，2-辛基巯基-4，6-双(3，5-二叔丁基-4-羟基苯胺基)-1，3，5-三嗪，2-辛基巯基-4，6-双(3，5-二叔丁基-4-羟基苯氧基)-1，3，5-三嗪，2，4，6-三-(3，5-二叔丁基-4-羟基苯氧基)-1，2，3-三嗪，1，3，5-三(3，5-二叔丁基-4-羟基苄基)异氰脲酸酯，1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)异氰脲酸酯，2，4，6-三(3，5-二叔丁基-4-羟基苯乙基)-1，3，5-三嗪，1，3，5-三(3，5-二叔丁基-4-羟基苯丙酰基)-六氢-1，3，5-三嗪或1，3，5-三(3，5-二环己基-4-羟基苄基)异氰脲酸酯。
11)苄基膦酸酯，例如2，5-二叔丁基-4-羟基苄基膦酸二甲酯，3，5-二叔丁基-4-羟基苄基膦酸二乙酯，3，5-二叔丁基-4-羟基苄基膦酸二-十八碳烷基酯，5-叔丁基-4-羟基-3-甲基苄基膦酸二-十八碳烷基酯，3，5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
12)酰基氨基酚类，例如，4-羟基月桂酰苯胺，4-羟基硬脂酰苯胺，N-(3，5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
13)β-(3，5-二叔丁基-4-羟基苯基)丙酸、β-(5-叔丁基-4-羟基-3-甲基 苯基)丙酸、β-(3，5-二环己基-4-羟基苯基)丙酸、3，5-二叔丁基-4-羟基 苯乙酸或β-(5-叔丁基-4-羟基苯基)-3-硫代丁酸与一元或多元醇形成的 酯类，例如与甲醇、乙醇、正辛醇、异辛醇、十八碳醇、1，6-己二醇、1，9-壬二醇、乙二醇、1，2-丙二醇、新戊基二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N，N′-双(羟乙基)草酰胺、3-硫杂十一碳醇、3-硫杂十五碳醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2，6，7-三氧杂双环(2.2.2)辛烷、甘油或以例如椰子油、菜籽油、葵花籽油或菜油的天然三酸甘油酯为基础的转酯化产物等所形成的酯类。
14)β-(3，5-二叔丁基-4-羟基苯基)丙酸的酰胺，例如，N，N′-双(3，5-二叔丁-4-羟基苯丙酰基)六亚甲基二胺、N，N′-双(3，5-二叔丁基-4-羟基苯丙酰基)三亚甲基二胺、N，N′-双-(3，5-二叔丁基-4-羟基苯丙酰基)肼。
15)抗坏血酸(维生素C)
16)胺类抗氧剂，例如N，N′-二异丙基-对苯二胺、N，N′-二仲丁基-对苯二胺、N，N′-双(1，4-二甲基戊基)-对苯二胺、N，N′-双(1-乙基-3-甲基戊基)对苯二胺、N，N′-双(1-甲基戊基)-对苯二胺、N，N′-二环己基对苯二胺、N，N′-二苯基-对苯二胺、N，N′-双(萘-2-基)对苯二胺、N-异丙基-N′-苯基-对苯二胺、N-(1，3-二甲基丁基)-N′-苯基对苯二胺、N-(1-甲基庚基)-N′-苯基-对苯二胺、N-环己基-N′-苯基-对苯二胺、4-(对甲苯氨磺酰基)二苯基胺、N，N′-二甲基-N，N′-二仲丁基-对苯二胺、二苯胺、N-烯丙基苯基胺、4-异丙氧基二苯基胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化的二苯基胺，例如p，p′-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰基氨基苯酚、4-十二碳酰基氨基苯酚、4-十八碳酰基-氨基苯酚、双(4-甲氧基苯基)胺、2，6-二叔丁基-4-二甲胺基甲基苯酚、2，4′-二氨基二苯基甲烷、4，4′-二氨基-二苯基甲烷、N，N，N′，N′-四甲基-4，4′-二氨基二苯基甲烷、1，2-双((2-甲基苯基)氨基)乙烷、1，2-双(苯基氨基)丙烷、(邻甲苯基)双胍、双(4-(1′，3′-二甲基丁基)苯基)胺、叔辛基化的N-苯基-1-萘胺，一和二烷基化的叔丁基/叔辛基二苯胺类的混合物，一和二烷基化的壬基二苯胺类的混合物，一和二烷基化的十二碳烷基二苯胺类的混合物，一和二烷基化的异丙基/异己基二苯胺类的混合物，一和二烷基化的叔丁基二苯胺类的混合物，2，3-二氢-3，3-二甲基-4H-1，4-苯并噻嗪，吩噻嗪，一和二烷基化的叔丁基/叔辛基吩噻嗪类的混合物，一和二烷基化的叔辛基吩噻嗪类的混合物，N-烯丙基吩噻嗪，N，N，N′，N′-四苯基-1，4-二氨基丁-2-烯，N，N-二(2，2，6，6-四甲基哌啶-4-基)六亚甲基二胺，二-(2，2，6，6-四甲基哌啶-4-基)癸二酸酯，2，2，6，6-四甲基哌啶-4-酮，或2，2，6，6-四甲基哌啶-4-醇，和
17)脂肪族或芳族亚磷酸酯，硫代二丙酸或硫代二乙酸的酯，或二硫代氨基甲酸或二硫代磷酸的盐，2，2，12，12-四甲基-5，9-二羟基-3，7，1-三硫代十三烷或2，2，15，15-四甲基-5，12-二羟基-3，7，10，14-四硫代十六烷。
适当的组分(c)的耐磨添加剂选自：
1)二烃基二硫代磷酸酯金属盐，其中所述金属是铝，铅，锡，锰，钴，镍，锌或铜，但往往大多数是锌。锌盐(二烷基二硫代磷酸锌)由下式表示：
其中R和R′独立地表示C1-C20烷基，C3-C20烯基，C5-C12环烷基，C7-C13芳烷基，或C6-C10芳基，例如，R和R′独立地为C1-C12烷基，和
2)含硫-和/或磷-和/或卤素的化合物，如硫化烯烃和植物油，磷酸三甲酚酯，磷酸三甲苯酯，氯化石蜡，烷基和芳基二和三硫化物，磷酸单-和二烷基酯的胺盐，甲基膦酸的胺盐，二乙醇氨基甲基甲苯基三唑，二(2-乙基己基)-氨甲基甲苯基三唑，2，5-二巯基-1，3，4-噻二唑的衍生物，((二异丙氧基硫膦基)硫代)丙酸乙酯，硫代磷酸三苯基酯(硫代磷酸三苯基酯)，硫代磷酸三(烷基苯基)酯和其混合物(例如三(异壬基苯基)硫代磷酸酯)，二苯基单壬基苯基硫代磷酸酯，异丁基苯基二苯基硫代磷酸酯，3-羟基-1，3-硫磷代庚烷-3-氧化物的十二烷基胺盐，三硫代磷酸-5，5，5-三(异辛基-2-乙酸酯)2-巯苯噻唑的衍生物，如1-(N，N-二(2-乙基己基)氨甲基)-2-巯基-1H-1，3-苯并噻唑或乙氧基羰基-5-辛基二硫代氨基甲酸酯。
适当的组分(c)的分散剂选自：
1)曼尼希碱，其为高分子量酚、亚烷基多胺和诸如甲醛的醛的缩合反应产物，
2)琥珀基分散剂，其为烯烃聚合物和琥珀酰化剂(酸、酸酐、酯或卤化物)的反应产物与有机羟基化合物和/或胺进一步反应的反应产物，和
3)高分子量酰胺和酯，如烃基酰化剂和多羟基脂族醇(如甘油、季戊四醇或山梨糖醇)的反应产物。
通常用作分散剂的是无灰(不含金属的)聚合物材料，该聚合物材料通常包含油溶性高分子量骨架，该骨架连接到与待分散颗粒缔合的极性官能团上。通常使用的烃骨架物质是烯烃聚合物和共聚物，即乙烯、丙烯、丁烯、异丁烯、苯乙烯；其中可以有或可以不必有另外的官能团引入到聚合物的骨架上。极性物质如胺、醇、酰胺或酯通过桥连接到所述骨架上。
适当的组分(c)的洗涤剂选自：有机酸的钙、镁、钡、钠或锂盐，例如磺酸盐、烷基酚盐、硫化的烷基酚盐、羧酸盐、水杨酸盐、膦酸盐、硫代膦酸盐和亚膦酸盐。所述盐可以是中性的或者可以通过，例如金属氢氧化物或碳酸盐过碱化。
适当的组分(c)的消泡添加剂选自：聚硅氧烷油，聚硅氧烷和聚乙二醇醚。
适当的组分(c)的粘度指数改进剂选自：聚异丁烯，乙烯和丙烯的共聚物，聚丙烯酸酯，聚甲基丙烯酸酯，乙烯基吡咯烷酮/甲基丙烯酸酯共聚物，聚乙烯吡咯烷酮，聚丁烯，烯烃共聚物，苯乙烯/丙烯酸酯共聚物，苯乙烯/异戊二烯共聚物，苯乙烯/异丁二烯共聚物，异戊二烯/丁二烯共聚物和聚醚。
适当的组分(c)的铜钝化剂选自：
1)苯并三唑和其衍生物，例如4-或5-烷基苯并三唑类(如甲苯并三唑)和其衍生物，4，5，6，7-四氢苯并三唑，5，5′-亚甲基-二苯并三唑；苯并三唑或甲苯并三唑的曼尼希碱，如1-(二(2-乙基已基)氨甲基)甲苯并三唑和1-(二(2-乙基己基)氨甲基)苯并三唑；烷氧基烷基苯并三唑类，如1-(壬氧基甲基)-苯并三唑，1-(1-丁氧基乙基)-苯并三唑或1-(1-环己氧基丁基)-甲苯并三唑，
2)咪唑衍生物，例如4，4′-亚甲基双(2-十一烷基-5-甲基咪唑)，二((N-甲基)咪唑-2-基)原醇辛基醚，
3)含硫杂环化合物，例如2-巯苯并噻唑，2，5-二巯基-1，3，4-噻二唑，2，5-二巯基-苯并噻二唑和其衍生物或3，5-双(二(2-乙基己基)氨甲基)-1，3，4-噻二唑啉-2-酮，和
4)氨基化合物，例如亚水杨基亚丙基二胺，水杨基氨基胍或其盐。
适当的组分(c)的防锈剂选自：
1)非离子的聚氧化烯多元醇和它们的酯，聚氧化烯酚，有机酸，它们的酯，金属盐，胺盐和酸酐，例如烷基-和烯基丁二酸和其与醇、二醇或羟基羧酸形成的偏酯，烷基-和烯基丁二酸部分酰胺，4-壬基苯氧基乙酸，烷氧基-和烷氧基乙氧基羧酸如十二烷氧基乙酸，十二烷氧基(乙氧基)乙酸和其胺盐，或N-油酰基肌氨酸，去水山梨糖醇单油酸酯，环烷酸铅和烯基丁二酸酐如十二烷基丁二酸酐，2-(2-羧乙基)-1-十二烷基-3-甲基甘油及其盐，例如钠和三乙醇胺盐，
2)含氮化合物，其选自：
i)有机和无机酸的伯、仲或叔脂肪族或环脂族的胺和胺盐，例如油溶性羧酸烷基铵盐，以及1-(N，N-二(2-羟乙基)氨基)-3-(4-壬基苯氧基)丙烷-2-醇，或
ii)杂环化合物，比如：取代的咪唑啉或噁唑啉，如2-十七烯基-1-(2-羟乙基)-咪唑啉，
3)含磷化合物，例如磷酸、磷酸偏酯或膦酸偏酯的胺盐或二烷基二硫代磷酸锌，
4)含硫化合物，例如二壬基萘磺酸钡，石油磺酸钙，烷硫基取代的脂族羧酸，脂肪族的2-磺基数酸的酯或其盐，和
5)甘油衍生物，例如甘油单油酸酯，1-(烷基苯氧基)-3-(2-羟乙基)甘油，1-(烷基苯氧基)-3-(2，3-二羟丙基)甘油或2-羧基烷基-1，3-二烷基甘油。
适当的组分(c)的倾点下降剂选自聚甲基丙烯酸酯和烷基化的萘衍生物。
适当的组分(c)的破乳剂选自烷基醚多醇和二壬基萘磺酸酯。
适当的组分(c)的摩擦改性剂选自脂肪酸和其衍生物，如脂肪酸的天然酯如甘油单油酸酯，酰胺，酰亚胺和胺如油胺，含硫有机二硫代氨基甲酸钼，含硫-磷的有机二硫代磷酸钼，基于分散剂的含硫-氮的有机钼化合物，羧酸钼盐，钼-胺络合物，钼-胺/醇/酰胺络合物和钼簇化合物，Teflon和二硫化钼。
对铅有腐蚀性的添加剂是抗氧化剂，抗磨剂，洗涤剂，铜钝化剂或摩擦改性剂，如含硫抗氧化剂，含硫抗磨剂，含硫的铜钝化剂或由植物油衍生的摩擦改性剂。例如，对铅有腐蚀性的含硫抗氧化剂是吩噻嗪抗氧化剂。
在所有情况下，组分(c)添加剂的惯常加入量为，以发动机油组合物计约0.01-约10.0重量％。
式(I)的化合物可以以本身已知的方式被引入到发动机油中。所述化合物很容易溶于油中。也可以制备所谓的添加剂母料(包装)，它们可以用相应的液体稀释以在其需要的比率浓度下使用。式(I)的化合物可以作为添加剂包的一部分引入。
在没有本发明式(I)化合物的情况下，含有组分(a)和(c)的发动机油当用ASTM D 6594测定时，不能满足或只是差不多满足ASTM D 4485中定义的铅腐蚀规格标准。也就是说，含有组分(a)和(c)的发动机油，在没有本发明式(I)化合物存在的情况下，在通过ASTM D 6594测定时，有超过约100ppm，约120ppm，约150ppm，约180ppm，或约210ppm(的铅)。
本发明也涉及一种在存在发动机油组合物的情况下防止铅制部件腐蚀的方法，所述发动机油组合物包括(a)基液，和(c)至少一种对铅具有腐蚀性的油添加剂，且该油添加剂选自抗氧化剂，抗磨剂，分散剂，洗涤剂，破乳剂和摩擦改性剂，该方法含有向所述发动机油组合物中引入(b)至少一种式(I)的化合物，其中在没有组分(b)的情况下，所述发动机油组合物在根据ASTM D 6594试验测定时铅超过约100ppm。
以下实施例更详细地说明本发明。它们不允许被视为以任何方式对本发明构成限定。
实施例
在135℃对腐蚀性柴油机油的ASTM D 6594评价
在这一试验中，将铜、铅、锡和磷青铜的金属试样浸于被测量的发动机油中。该油，在135℃下鼓气168小时。当试验结束时，检测受压油以检查腐蚀性和腐蚀产物。通过ICP测定用过的油中是否存在铜、铅和锡。在受压油中铅低于50ppm时，这样的结果是所希望的。
完全调配的、无腐蚀性的发动机油用作用于这一实施例的基本配方。
为了举例说明本发明的效果，分别将1.0重量％的摩擦改性剂/缓蚀剂，甘油单油酸酯(GMO)和0.5重量％的含硫抗磨/极压添加剂，二叔壬基三硫化物(TPS27)加入到基本配方中。在有和没有加0.2重量％的式(1)化合物：1-(二(2-乙基己基)氨甲基)-1，2，4-三唑(Irgamet30，Ciba Specialty Chem.)的情况下，均对这些进行各自的ASTM D 6594试验。
| 无IRGAMET 30 | 有IRGAMET 30 | |
| 1)基本配方 | 75ppm | --- |
| 2)(1)加1.0％的GMO | 358ppm | 29ppm |
| 3)(1)加0.5％的TPS 27 | 117ppm | 43ppm |
GMO和TPS27两者都会加剧基本配方的腐蚀性，这使得它们不适合于使用。在所有情况下，IRGAMET 30均显著地将腐蚀降低到极其可接受的程度。
Claims (10)
1.一种对于铅制品不具有侵蚀性的发动机油组合物，该组合物包含：
(a)基液，
(b)至少一种式(I)的化合物，
(c)至少一种对于铅制品有腐蚀性的油添加剂，所述油添加剂选自抗氧化剂，耐磨添加剂，分散剂，洗涤剂，消泡添加剂，粘度指数改进剂，铜钝化剂，防锈剂，降凝剂，破乳剂和摩擦改性剂，
其中：
R1和R2相同或不同，是C1-C20烷基，C3-C20烯基，C5-C12环烷基，C7-C13芳烷基，或C6-C10芳基，或R1和R2与和它们各自连接的氮原子一起可以形成5-、6-或7-元杂环残基，或R1和R2是下式的基团：
R3X[(-R4-)O]n(-R4)-
其中：
X是O、S或N，
R3是氢或C1-C20烷基，
R4是C1-C12亚烷基，
n是0或1-6的整数，
或R1和R2中的一个是下式(II)的基团：
或R2是式(II)的基团而R1是下式的基团：
-[R4]n-N(R5)-A-[N(R5)2]m
其中：
m是0或1，且当m是0时，A是式(II)的基团，当m是1时，A是亚烷基或C6-C10亚芳基，R5是式(II)的基团，并且，当在没有组分(b)的情况下，该发动机油组合物在根据ASTM D 6594试验测定时铅超过约100ppm。
2.根据权利要求1的组合物，其中式(I)化合物选自；
1-(或4)-(二甲基氨甲基)三唑；
1-(或4)-(二乙基氨甲基)三唑；
1-(或4)-(二异丙基氨甲基)三唑；
1-(或4)-(二正丁基氨甲基)三唑；
1-(或4)-(二正己基氨甲基)三唑；
1-(或4)-(二异辛基氨甲基)三唑；
1-(或4)-(二(2-乙基己基)氨甲基)三唑；
1-(或4)-(二正辛基氨甲基)三唑；
1-(或4)-(二正癸基氨甲基)三唑；
1-(或4)-(二正十二烷基氨甲基)三唑；
1-(或4)-(二正十八烷基氨甲基)三唑；
1-(或4)-(二正二十烷基氨甲基)三唑；
1-(或4)-[二(丙-2′-烯基)氨甲基]三唑；
1-(或4)-[二(丁-2′-烯基)氨甲基]三唑；
1-(或4)-[二(二十-2′-烯基)氨甲基]三唑；
1-(或4)-(二环己基氨甲基)三唑；
1-(或4)-(二苄基氨甲基)三唑；
1-(或4)-(二苯基氨甲基)三唑；
1-(或4)-(4′-吗啉甲基)三唑；
1-(或4)-(1’-吡咯烷甲基)三唑；
1-(或4)-(1’-哌啶甲基)三唑；
1-(或4)-(1’-全氢氮杂甲基)三唑；
1-(或4)-(2′，2″-二羟乙基)氨甲基]三唑；
1-(或4)-(二丁氧基丙基氨甲基)三唑；
1-(或4)-(二丁硫基丙基氨甲基)三唑；
1-(或4)-(二丁氨基丙基氨甲基)三唑；
N，N-二(1-或4-三唑基甲基)月桂胺；
N，N-二(1-或4-三唑基甲基)油胺；
N，N-二(1-或4-三唑基甲基)乙醇胺和
N，N，N′，N′-四-(1-或4-三唑基甲基)乙二胺。
3.根据权利要求1的组合物，其中式(I)化合物是1-(二异辛基氨甲基)-1，2，4-三唑，或1-(二(2-乙基己基)氨甲基)-1，2，4-三唑。
4.根据权利要求1的组合物，其中组分(b)的存在量为以发动机油的重量计约0.01-约1.0重量％。
5.根据权利要求1的组合物，其中组分(b)的存在量为以发动机油的重量计约0.02-约0.5重量％。
6.根据权利要求1的组合物，其中组分(b)的存在量为以发动机油的重量计约0.03-约0.3重量％。
7.根据权利要求1的组合物，其中组分(c)的添加剂选自抗氧化剂，耐磨添加剂，洗涤剂，铜钝化剂和摩擦改性剂。
8.根据权利要求1的组合物，其中组分(c)的添加剂选自含硫抗氧化剂，含硫耐磨添加剂，含硫铜钝化剂和由植物油衍生的摩擦改性剂。
9.根据权利要求1的组合物，其中组分(c)的添加剂选自酚噻嗪抗氧化剂和由植物油衍生的摩擦改性剂。
10.一种在存在发动机油组合物的情况下防止铅制部件腐蚀的方法，所述发动机油组合物包括(a)基液，和(c)至少一种对铅具有腐蚀性的油添加剂，且该油添加剂选自抗氧化剂，耐磨添加剂，分散剂，洗涤剂，消泡添加剂，粘度指数改进剂，铜钝化剂，防锈剂，降凝剂，破乳剂和摩擦改性剂，该方法含有向所述发动机油组合物中引入(b)至少一种根据权利要求1的式(I)的化合物，其中在没有组分(b)的情况下，所述发动机油组合物在根据ASTM D 6594试验测定时铅超过约100ppm。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40129902P | 2002-08-06 | 2002-08-06 | |
| US60/401,299 | 2002-08-06 |
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| CN1675341A true CN1675341A (zh) | 2005-09-28 |
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| US (1) | US20040038835A1 (zh) |
| EP (1) | EP1532232A1 (zh) |
| JP (1) | JP2005534782A (zh) |
| KR (1) | KR20050032104A (zh) |
| CN (1) | CN1675341A (zh) |
| AU (1) | AU2003253351B2 (zh) |
| BR (1) | BR0313248A (zh) |
| CA (1) | CA2494639A1 (zh) |
| MX (1) | MXPA05001129A (zh) |
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| WO (1) | WO2004015043A1 (zh) |
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| CN101454429B (zh) * | 2006-05-23 | 2012-08-08 | 西巴控股有限公司 | 用于有色金属的腐蚀抑制组合物 |
| CN104232185A (zh) * | 2009-07-13 | 2014-12-24 | 乔治洛德方法研究和开发液化空气有限公司 | 用于燃料的杀菌和防腐蚀添加的添加剂混合物 |
| CN107922870A (zh) * | 2015-08-14 | 2018-04-17 | 范德比尔特化学品有限责任公司 | 包含含硫和无硫有机钼化合物和三唑的润滑剂组合物添加剂 |
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| US7732389B2 (en) * | 2005-02-04 | 2010-06-08 | Exxonmobil Chemical Patents Inc. | Lubricating fluids with low traction characteristics |
| US20060264341A1 (en) * | 2005-05-20 | 2006-11-23 | Culley Scott A | Transmission composition |
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| EP2011853A4 (en) * | 2006-03-31 | 2014-04-16 | Idemitsu Kosan Co | LUBRICATING OIL ADDITIVE, LUBRICATING OIL COMPOSITION CONTAINING SAME, VARIOUS LOW FRICTION SLIDING ELEMENTS, BEARING BEARING AND SMOOTH BEARING |
| ES2301358B1 (es) | 2006-05-12 | 2009-06-22 | Repsol Ypf, S.A. | Nueva composicion de combustible estabilizado. |
| JP2010511067A (ja) * | 2006-11-27 | 2010-04-08 | チバ ホールディング インコーポレーテッド | 安定化されたバイオディーゼル燃料組成物 |
| US20080139425A1 (en) * | 2006-12-11 | 2008-06-12 | Hutchison David A | Lubricating composition |
| EP2118245A2 (en) * | 2007-02-07 | 2009-11-18 | Ciba Holding Inc. | Multiple metal corrosion inhibitor |
| US20090042752A1 (en) * | 2007-08-09 | 2009-02-12 | Malcolm Waddoups | Lubricant Compositions with Reduced Phosphorous Content for Engines having Catalytic Converters |
| WO2010053893A1 (en) * | 2008-11-05 | 2010-05-14 | The Lubrizol Corporation | Method of lubricating an internal combustion engine |
| EP2398875B1 (en) | 2009-02-18 | 2017-08-09 | The Lubrizol Corporation | Composition containing ester compounds and a method of lubricating an internal combustion engine |
| WO2010096291A1 (en) | 2009-02-18 | 2010-08-26 | The Lubrizol Corporation | Compounds and a method of lubricating an internal combustion engine |
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| US8236205B1 (en) | 2011-03-11 | 2012-08-07 | Wincom, Inc. | Corrosion inhibitor compositions comprising tetrahydrobenzotriazoles and other triazoles and methods for using same |
| US8236204B1 (en) | 2011-03-11 | 2012-08-07 | Wincom, Inc. | Corrosion inhibitor compositions comprising tetrahydrobenzotriazoles solubilized in activating solvents and methods for using same |
| KR101234275B1 (ko) * | 2011-03-21 | 2013-02-18 | 한국화학연구원 | 트리아졸 함유 숙신산 에스테르 화합물 및 그를 포함하는 방청제 |
| JP5771103B2 (ja) * | 2011-09-16 | 2015-08-26 | 昭和シェル石油株式会社 | 潤滑油組成物 |
| EP3334811A1 (en) * | 2015-08-14 | 2018-06-20 | Vanderbilt Chemicals, LLC | Novel alkylated diphenylamine derivatives of triazole and lubricating compositions containing the same |
| EP3802750A1 (en) * | 2018-06-08 | 2021-04-14 | The Lubrizol Corporation | Vapor phase corrosion inhibition |
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| GB1111680A (en) * | 1965-12-01 | 1968-05-01 | Shell Int Research | Improvements in or relating to ester-base compositions |
| US4491527A (en) * | 1982-04-26 | 1985-01-01 | The Lubrizol Corporation | Ester-heterocycle compositions useful as "lead paint" inhibitors in lubricants |
| GB8408617D0 (en) * | 1984-04-04 | 1984-05-16 | Ciba Geigy Ag | Metal deactivators |
| CA2105132A1 (en) * | 1992-09-28 | 1994-03-29 | John W. Frankenfeld | Substituted 1, 2, 4-triazole containing lubricants having improved oxidation stability |
| US5580482A (en) * | 1995-01-13 | 1996-12-03 | Ciba-Geigy Corporation | Stabilized lubricant compositions |
| JP3654371B2 (ja) * | 1995-02-27 | 2005-06-02 | 出光興産株式会社 | ディーゼル軽油組成物 |
| EP1054052B1 (en) * | 1999-05-19 | 2006-06-28 | Ciba SC Holding AG | Stabilized hydrotreated and hydrodewaxed lubricant compositions |
| US6207623B1 (en) * | 2000-01-14 | 2001-03-27 | Exxonmobil Research And Engineering Company | Industrial oils of enhanced resistance to oxidation |
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2003
- 2003-06-19 US US10/465,423 patent/US20040038835A1/en not_active Abandoned
- 2003-07-29 KR KR1020057001865A patent/KR20050032104A/ko not_active Application Discontinuation
- 2003-07-29 MX MXPA05001129A patent/MXPA05001129A/es active IP Right Grant
- 2003-07-29 AU AU2003253351A patent/AU2003253351B2/en not_active Ceased
- 2003-07-29 BR BR0313248-0A patent/BR0313248A/pt not_active IP Right Cessation
- 2003-07-29 CN CNA038188643A patent/CN1675341A/zh active Pending
- 2003-07-29 EP EP03784098A patent/EP1532232A1/en not_active Withdrawn
- 2003-07-29 WO PCT/EP2003/008352 patent/WO2004015043A1/en active Application Filing
- 2003-07-29 JP JP2004526808A patent/JP2005534782A/ja active Pending
- 2003-07-29 CA CA002494639A patent/CA2494639A1/en not_active Abandoned
- 2003-08-04 TW TW092121255A patent/TW200413518A/zh unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454429B (zh) * | 2006-05-23 | 2012-08-08 | 西巴控股有限公司 | 用于有色金属的腐蚀抑制组合物 |
| CN104232185A (zh) * | 2009-07-13 | 2014-12-24 | 乔治洛德方法研究和开发液化空气有限公司 | 用于燃料的杀菌和防腐蚀添加的添加剂混合物 |
| CN104232185B (zh) * | 2009-07-13 | 2017-05-10 | 乔治洛德方法研究和开发液化空气有限公司 | 用于燃料的杀菌和防腐蚀添加的添加剂混合物 |
| CN107922870A (zh) * | 2015-08-14 | 2018-04-17 | 范德比尔特化学品有限责任公司 | 包含含硫和无硫有机钼化合物和三唑的润滑剂组合物添加剂 |
| CN107922869A (zh) * | 2015-08-14 | 2018-04-17 | 范德比尔特化学品有限责任公司 | 用于包含有机钼化合物和衍生化三唑的润滑剂组合物的添加剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003253351B2 (en) | 2009-07-02 |
| AU2003253351A1 (en) | 2004-02-25 |
| KR20050032104A (ko) | 2005-04-06 |
| JP2005534782A (ja) | 2005-11-17 |
| TW200413518A (en) | 2004-08-01 |
| MXPA05001129A (es) | 2005-05-16 |
| WO2004015043A1 (en) | 2004-02-19 |
| BR0313248A (pt) | 2005-07-12 |
| EP1532232A1 (en) | 2005-05-25 |
| US20040038835A1 (en) | 2004-02-26 |
| CA2494639A1 (en) | 2004-02-19 |
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