CA2572041A1 - A method of improving the acrylic rubber sealant compatibility with a lubricating oil composition in an internal combustion engine in comparison to a conventionally used lubricating oil composition - Google Patents
A method of improving the acrylic rubber sealant compatibility with a lubricating oil composition in an internal combustion engine in comparison to a conventionally used lubricating oil composition Download PDFInfo
- Publication number
- CA2572041A1 CA2572041A1 CA002572041A CA2572041A CA2572041A1 CA 2572041 A1 CA2572041 A1 CA 2572041A1 CA 002572041 A CA002572041 A CA 002572041A CA 2572041 A CA2572041 A CA 2572041A CA 2572041 A1 CA2572041 A1 CA 2572041A1
- Authority
- CA
- Canada
- Prior art keywords
- lubricating oil
- oil composition
- amount
- content
- metal
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 101
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000004589 rubber sealant Substances 0.000 title claims abstract description 24
- 229920000800 acrylic rubber Polymers 0.000 title claims abstract description 21
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 21
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003599 detergent Substances 0.000 claims abstract description 45
- -1 alkali metal salt Chemical class 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- 239000002585 base Substances 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 239000002199 base oil Substances 0.000 claims description 32
- 150000001340 alkali metals Chemical class 0.000 claims description 22
- 229960002317 succinimide Drugs 0.000 claims description 22
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 230000001050 lubricating effect Effects 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- 239000005078 molybdenum compound Substances 0.000 claims description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 6
- 150000003871 sulfonates Chemical class 0.000 claims description 6
- 125000005266 diarylamine group Chemical group 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012990 dithiocarbamate Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003580 thiophosphoric acid esters Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 description 26
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 23
- 229910052791 calcium Inorganic materials 0.000 description 18
- 239000000654 additive Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 12
- 239000000565 sealant Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- QHPKIUDQDCWRKO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 QHPKIUDQDCWRKO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-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
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- RKLRVTKRKFEVQG-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 RKLRVTKRKFEVQG-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- LMODBLQHQHXPEI-UHFFFAOYSA-N dibutylcarbamothioylsulfanylmethyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SCSC(=S)N(CCCC)CCCC LMODBLQHQHXPEI-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- BRESEFMHKFGSDY-UHFFFAOYSA-N molybdenum;pyrrolidine-2,5-dione Chemical compound [Mo].O=C1CCC(=O)N1 BRESEFMHKFGSDY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- HUNGQTAXBUKZGQ-UHFFFAOYSA-N tripotassium borate hydrate Chemical compound O.[K+].[K+].[K+].[O-]B([O-])[O-] HUNGQTAXBUKZGQ-UHFFFAOYSA-N 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 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
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
-
- 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
- C10M2205/024—Propene
-
- 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
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- 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
- C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
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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
- C10M2215/28—Amides; Imides
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/043—Mannich bases
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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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
- 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
- C10M2219/046—Overbased sulfonic acid salts
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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
- C10M2223/045—Metal containing thio derivatives
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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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
- Sealing Material Composition (AREA)
Abstract
It has been discovered that a lubricating oil composition containing a certain combination of a nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure, together with a phosphorus-containing organic compound, can be effectively employed in a method for improving the acrylic rubber sealant compatibility in an internal combustion engine, if the ratio of the nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure is adjusted to a specific range, i.e., in the range of from 1:0.005 to 1:2 in terms of the nitrogen content.
Description
A METHOD OF IMPROVING THE ACRYLIC RUBBER SEALANT
COMPATIBILITY IN AN I-NTERNAL COMBUSTION ENGINE
The present invention relates to a method of improving the acrylic rubber sealant compatibility in an internal combustion engine. More specifically, the present invention relates to a method comprising contacting acrylic rubber sealants in an internal combustion engine and operating the internal combustion engine with a lubricating oil composition having improved acrylic rubber sealant compatibility.
BACKGROUND OF THE INVENTION
In mechanical devices such as internal-combustion engine vehicles and various other industrial machines, it is necessary to supply a lubricating oil to mechanisms involving rubbing movement. Lubrication systems for supplying a lubricating oil are generally equipped with various sealing materials (sealants).
Examples of the sealing materials include resin or rubber sealants such as silicone rubber sealant, acrylic rubber sealant, fluorocarbon resin sealant, nitrile rubber sealant, hydrogenated nitrile rubber sealant and ethylene-propylene rubber sealant. According to their physical and chemical characteristics, those sealants are optionally selected to be installed in proper parts of the lubrication systems. Among the above-mentioned materials, acrylic rubber sealant is particularly used as packing parts for fixation because it is not only excellent in heat resistance and oil resistance but also inexpensive, At the present time, it is required to improve lubricating oils for the purpose of meeting certain performance requirements. Most lubricating oils contacting rubbing mechanisms in various machines are nowadays high-performance lubricating oil compositions comprising a lubricating base oil and various additives added thereto.
However, lubricating oil compositions containing various additives often deteriorate resin or rubber sealants despite satisfying lubricating performance requirements. Most of the additives contained in the compositions are so chemically active that they are liable to shrink the sealants and/or to impair their strength and elasticity.
Accordingly, it is desirable to have a lubricating oil composition which satisfies the severe performance requirements concerning lubricating oil compositions and, at the same time, which hardly impairs sealing performance of the sealants themselves.
U.S. Patent No. 6,124,247 describes a lubricating oil composition containing a borated glycerol ester and a mono-succinimide or bis-succinimide type dispersant subjected or not subjected to post-treatment with, for example, ethylene carbonate. It is stated that this oil composition has excellent compatibility with fluorocarbon elastomer, which is used as a sealant in a lubrication system of an internal-combustion engine.
JP-A-1 1-181461 describes that a lubricating oil composition containing an aliphatic amine has excellent compatibility with rubber sealants.
U.S. Patent No. 6,569,818 describes a lubricating oil composition containing an ashless dispersant of an alkenyl- or alkyl-succinic imide or a derivative thereof, an alkali metal or alkaline earth metal alkylsalicylate of non-sulfide or otherwise an alkali metal salt of alkylphenol derivative having a Mannich base structure, a zinc dialkyldithiophosphate, and an oxidation inhibiting phenol or amine compound. It is stated that all of the ash content, the phosphorus content and the sulfur content of the disclosed lubricating oil composition are low levels and that the lubricating oil composition gives high detergency at a high temperature.
U.S.
Patent No. 6,569,818, however, is silent about a lubricating oil composition of the present invention described hereinbelow. Further, this reference neither describes nor suggests any effect that the lubricating oil composition has on sealants.
SUMMARY OF THE INVENTION
The present invention relates to a method of improving acrylic rubber sealant compatibility in an internal combustion engine. The method involves contacting the acrylic rubber sealant in the internal combustion engine and operating the internal combustion engine with a lubricating oil composition comprising:
a) a major amount of a base oil of lubricating viscosity, b) a nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.%, preferably 0.01 to 0.1 wt.%, in terms of the nitrogen content, based on the total amount of the lubricating oil composition, c) a metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure in an amount of 0.001 to 0.4 wt.%, preferably 0.002 to 0.1 wt.%, in terms of the metal content, based on the total amount of the lubricating oil composition, and d) a phosphorus-containing organic compound in an amount of 0.001 to 0.5 wt.%, preferably 0.01 to 0.2 wt.%, in terms of the phosphorus content, based on the total amount of the lubricating oil composition, wherein the ratio of components b) to c) is in the range of from 1:0.005 to 1:2, preferably 0:0.01 to 1:0.3, in terms of the nitrogen content.
The nitrogen-containing ashless dispersant in the lubricating oil composition employed in the method of the present invention is an alkenyl- or alkyl-succinic imide or a derivative thereof.
COMPATIBILITY IN AN I-NTERNAL COMBUSTION ENGINE
The present invention relates to a method of improving the acrylic rubber sealant compatibility in an internal combustion engine. More specifically, the present invention relates to a method comprising contacting acrylic rubber sealants in an internal combustion engine and operating the internal combustion engine with a lubricating oil composition having improved acrylic rubber sealant compatibility.
BACKGROUND OF THE INVENTION
In mechanical devices such as internal-combustion engine vehicles and various other industrial machines, it is necessary to supply a lubricating oil to mechanisms involving rubbing movement. Lubrication systems for supplying a lubricating oil are generally equipped with various sealing materials (sealants).
Examples of the sealing materials include resin or rubber sealants such as silicone rubber sealant, acrylic rubber sealant, fluorocarbon resin sealant, nitrile rubber sealant, hydrogenated nitrile rubber sealant and ethylene-propylene rubber sealant. According to their physical and chemical characteristics, those sealants are optionally selected to be installed in proper parts of the lubrication systems. Among the above-mentioned materials, acrylic rubber sealant is particularly used as packing parts for fixation because it is not only excellent in heat resistance and oil resistance but also inexpensive, At the present time, it is required to improve lubricating oils for the purpose of meeting certain performance requirements. Most lubricating oils contacting rubbing mechanisms in various machines are nowadays high-performance lubricating oil compositions comprising a lubricating base oil and various additives added thereto.
However, lubricating oil compositions containing various additives often deteriorate resin or rubber sealants despite satisfying lubricating performance requirements. Most of the additives contained in the compositions are so chemically active that they are liable to shrink the sealants and/or to impair their strength and elasticity.
Accordingly, it is desirable to have a lubricating oil composition which satisfies the severe performance requirements concerning lubricating oil compositions and, at the same time, which hardly impairs sealing performance of the sealants themselves.
U.S. Patent No. 6,124,247 describes a lubricating oil composition containing a borated glycerol ester and a mono-succinimide or bis-succinimide type dispersant subjected or not subjected to post-treatment with, for example, ethylene carbonate. It is stated that this oil composition has excellent compatibility with fluorocarbon elastomer, which is used as a sealant in a lubrication system of an internal-combustion engine.
JP-A-1 1-181461 describes that a lubricating oil composition containing an aliphatic amine has excellent compatibility with rubber sealants.
U.S. Patent No. 6,569,818 describes a lubricating oil composition containing an ashless dispersant of an alkenyl- or alkyl-succinic imide or a derivative thereof, an alkali metal or alkaline earth metal alkylsalicylate of non-sulfide or otherwise an alkali metal salt of alkylphenol derivative having a Mannich base structure, a zinc dialkyldithiophosphate, and an oxidation inhibiting phenol or amine compound. It is stated that all of the ash content, the phosphorus content and the sulfur content of the disclosed lubricating oil composition are low levels and that the lubricating oil composition gives high detergency at a high temperature.
U.S.
Patent No. 6,569,818, however, is silent about a lubricating oil composition of the present invention described hereinbelow. Further, this reference neither describes nor suggests any effect that the lubricating oil composition has on sealants.
SUMMARY OF THE INVENTION
The present invention relates to a method of improving acrylic rubber sealant compatibility in an internal combustion engine. The method involves contacting the acrylic rubber sealant in the internal combustion engine and operating the internal combustion engine with a lubricating oil composition comprising:
a) a major amount of a base oil of lubricating viscosity, b) a nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.%, preferably 0.01 to 0.1 wt.%, in terms of the nitrogen content, based on the total amount of the lubricating oil composition, c) a metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure in an amount of 0.001 to 0.4 wt.%, preferably 0.002 to 0.1 wt.%, in terms of the metal content, based on the total amount of the lubricating oil composition, and d) a phosphorus-containing organic compound in an amount of 0.001 to 0.5 wt.%, preferably 0.01 to 0.2 wt.%, in terms of the phosphorus content, based on the total amount of the lubricating oil composition, wherein the ratio of components b) to c) is in the range of from 1:0.005 to 1:2, preferably 0:0.01 to 1:0.3, in terms of the nitrogen content.
The nitrogen-containing ashless dispersant in the lubricating oil composition employed in the method of the present invention is an alkenyl- or alkyl-succinic imide or a derivative thereof.
The metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative in the lubricating oil composition employed in the method of the present invention has a Mannich base structure represented by the following formula:
OCaOH
CaOH *CH
N / C
wherein R is an alkyl group having 8 to 30 carbon atoms, and n is 0 or a positive integer.
The lubricating oil composition employed in the method of the present invention may further comprise a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
The lubricating oil composition employed in the method of the present invention may further comprise a metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content.
The amount of metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content.
OCaOH
CaOH *CH
N / C
wherein R is an alkyl group having 8 to 30 carbon atoms, and n is 0 or a positive integer.
The lubricating oil composition employed in the method of the present invention may further comprise a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
The lubricating oil composition employed in the method of the present invention may further comprise a metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content.
The amount of metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content.
The lubricating oil composition employed in the method of the present invention may further comprise a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in amount of 0.25 wt.% or less in terms of the molybdenum content.
The lubricating oil composition employed in the method of the present invention may further comprise an alkali metal borate in an amount of 2 wt.% or less and an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less.
The base oil of lubricating viscosity contains 10 wt.% or more of a mineral oil showing the following characteristics:
- 17 wt.% or less evaporation loss according to ASTM D-5800, - 90 wt.% or more saturated content, - 10 wt.% or less, aromatic component, - 0.01 wt.% or less, sulfur content, and - 120 or more viscosity index.
The lubricating oil composition employed in the method of the present invention is a SAE viscosity grade selected from the group consisting of 0W20, 0W30, 5W20, 5W30 and 10W30. Preferably, the lubricating oil composition meets the SAE 10W-30 viscosity grade.
Among other aspects, it has been discovered that a lubricating oil composition containing a certain combination of a nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure, together with a phosphorus-containing organic compound, can be effectively employed in a method for improving the acrylic rubber sealant compatibility in an internal combustion engine, if the ratio of the nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure is adjusted to a specific range, i.e., in the range of from 1:0.005 to 1:2 in terms of the nitrogen content. The lubricating oil composition hardly impairs the sealing performance of the acrylic rubber sealant.
DETAILED DESCRIPTION OF THE INVENTION
The present invention resides in a method of employing a certain lubricating oil composition to improve the acrylic rubber sealant compatibility in an internal combustion engine. The lubricating oil composition, while meeting the lubricating performance requirements of internal combustion engines, at the same time is less detrimental to the sealing performance of acrylic rubber sealants found in internal combustion engines as compared to conventionally used lubricating oil compositions. Thus, the method of the present invention advantageously improves the acrylic rubber sealant compatibility in internal combustion engines.
The preferred embodiments of the present invention will be described in further detail below. It should be noted that when weight percent is used herein, it is based on the total weight percent of the lubricating oil composition unless otherwise specified.
The lubricating oil composition employed in the method of the present invention will contain a nitrogen-containing ashiess dispersant. The nitrogen-containing ashless dispersant is preferably is a polyolefin-derived alkenyl- or alkyl-succinic imide or a derivative thereof. The amount of the nitrogen-containing ashless dispersant is in the range of 0.01 to 0.3 wt.%, preferably 0.01 to 0.1wt.%, in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
The lubricating oil composition employed in the method of the present invention may further comprise an alkali metal borate in an amount of 2 wt.% or less and an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less.
The base oil of lubricating viscosity contains 10 wt.% or more of a mineral oil showing the following characteristics:
- 17 wt.% or less evaporation loss according to ASTM D-5800, - 90 wt.% or more saturated content, - 10 wt.% or less, aromatic component, - 0.01 wt.% or less, sulfur content, and - 120 or more viscosity index.
The lubricating oil composition employed in the method of the present invention is a SAE viscosity grade selected from the group consisting of 0W20, 0W30, 5W20, 5W30 and 10W30. Preferably, the lubricating oil composition meets the SAE 10W-30 viscosity grade.
Among other aspects, it has been discovered that a lubricating oil composition containing a certain combination of a nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure, together with a phosphorus-containing organic compound, can be effectively employed in a method for improving the acrylic rubber sealant compatibility in an internal combustion engine, if the ratio of the nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure is adjusted to a specific range, i.e., in the range of from 1:0.005 to 1:2 in terms of the nitrogen content. The lubricating oil composition hardly impairs the sealing performance of the acrylic rubber sealant.
DETAILED DESCRIPTION OF THE INVENTION
The present invention resides in a method of employing a certain lubricating oil composition to improve the acrylic rubber sealant compatibility in an internal combustion engine. The lubricating oil composition, while meeting the lubricating performance requirements of internal combustion engines, at the same time is less detrimental to the sealing performance of acrylic rubber sealants found in internal combustion engines as compared to conventionally used lubricating oil compositions. Thus, the method of the present invention advantageously improves the acrylic rubber sealant compatibility in internal combustion engines.
The preferred embodiments of the present invention will be described in further detail below. It should be noted that when weight percent is used herein, it is based on the total weight percent of the lubricating oil composition unless otherwise specified.
The lubricating oil composition employed in the method of the present invention will contain a nitrogen-containing ashiess dispersant. The nitrogen-containing ashless dispersant is preferably is a polyolefin-derived alkenyl- or alkyl-succinic imide or a derivative thereof. The amount of the nitrogen-containing ashless dispersant is in the range of 0.01 to 0.3 wt.%, preferably 0.01 to 0.1wt.%, in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
A representative succinic imide can be prepared by the reaction between succinic anhydride having a high molecular weight alkenyl or alkyl substituent group with polyalkylenepolyamine containing 4 to 10 nitrogen atoms on average, preferably 5 to 7 nitrogen atoms. The high molecular weight alkenyl or alkyl substituent group is preferably a polybutene having a number average molecular weight of approximately 900 to 5,000.
The process for preparing the polybutenyisuccinic anhydride by the reaction between polybutene and maleic anhydride is generally performed by a chlorination method utilizing chlorine. While this reaction is advantageous in giving a high reaction yield, it has a disadvantageous feature in that a large amount (for instance, approximately 2,000 to 3,000 ppm) of chlorine remains in the final succinic imide product. In contrast, a thermal reaction process utilizing no chlorine can give a final reaction product having an extremely low chlorine content (such as 0 to 30 ppm). It is, therefore, preferred to use a succinic imide derived from the polybutenylsuccinic anhydride prepared by the thermal reaction process so that the chlorine content can be in the range of 0 to 30 ppm. The resulting succinic imide can be further converted into a modified succinic imide by a further reaction with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate or organic acids. From the thermal stability and oxidation stability, particularly preferred is a boron-containing alkenyl- or alkyl-succinic imide which is produced by the reaction with boric acid or a boron-containing compound.
The lubricating oil composition employed in the method of the present invention indispensably contains the ashless dispersant, whose representative example is an alkenyl- or alkyl-succinic imide or a derivative thereof. As the ashless dispersant, ashiess dispersants of alkenylbenzylamine type and alkenylsuccinic acid ester type can be also used.
The process for preparing the polybutenyisuccinic anhydride by the reaction between polybutene and maleic anhydride is generally performed by a chlorination method utilizing chlorine. While this reaction is advantageous in giving a high reaction yield, it has a disadvantageous feature in that a large amount (for instance, approximately 2,000 to 3,000 ppm) of chlorine remains in the final succinic imide product. In contrast, a thermal reaction process utilizing no chlorine can give a final reaction product having an extremely low chlorine content (such as 0 to 30 ppm). It is, therefore, preferred to use a succinic imide derived from the polybutenylsuccinic anhydride prepared by the thermal reaction process so that the chlorine content can be in the range of 0 to 30 ppm. The resulting succinic imide can be further converted into a modified succinic imide by a further reaction with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate or organic acids. From the thermal stability and oxidation stability, particularly preferred is a boron-containing alkenyl- or alkyl-succinic imide which is produced by the reaction with boric acid or a boron-containing compound.
The lubricating oil composition employed in the method of the present invention indispensably contains the ashless dispersant, whose representative example is an alkenyl- or alkyl-succinic imide or a derivative thereof. As the ashless dispersant, ashiess dispersants of alkenylbenzylamine type and alkenylsuccinic acid ester type can be also used.
The lubricating oil composition employed in the method of the present invention will contain metal-containing detergent of an alkali metal or alkaline metal earth metal salt of alkylphenol derivative. The metal-containing detergent of an alkali metal or alkaline metal earth metal salt of alkylphenol derivative has a Mannich base structure represented by the following formula:
CaOH CaOH CaOH
N
R n R
The amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of 0.001 to 0.4 wt.% in terms of the metal content or 0.002 to 0.1 wt.%
in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
The metal-containing detergent of an alkali metal (e.g., sodium, potassium) or alkaline earth metal (e.g., calcium, barium, magnesium) salt of alkylphenol derivative having a Mannich base structure, is generally prepared by the steps of:
synthesizing an intermediate having aminomethylated phenol ring by Mannich reaction from alkylphenol, formaldehyde, amine or an amine compound; and neutralizing the synthesized intermediate with a base such as calcium hydroxide to covert it into a metal salt. Examples include the compound of the above formula having the following characteristics:
Ca content: 2.5 wt.%, N content: 1.6 wt.%, total base number: 135 mg=KOH/g, and base number attributable to basic nitrogen: approximately 50% of the total base number.
The ratio of the nitrogen-containing ashless dispersant to the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of from 1:0.005 to 1:2, preferably 1:0.01 to 1:0.3, in terms of the nitrogen content.
The lubricating oil composition employed in the method of the present invention will contain a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
The amount of the phosphorus-containing organic compound is in the range of 0.001 to 0.5 wt.%, preferably 0.01 to 0.2 wt.%, in terms of the phosphorus content, based on the total amount of the lubricating oil composition.
Examples of the phosphorus-containing organic compounds include zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters in which each ester is generally derived from the corresponding acid and an alkylalcohol having 3 to 18 carbon atoms or an alkylarylalcohol having an alkyl group of 3 to 18 carbon atoms. If a zinc dihydrocarbyldithiophosphate (zinc dialkyldithiophosphate) is added, the amount of the additive is preferably in the range of 0.01 to 0.1 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition. From the viewpoint of reducing the phosphorus content and the sulfur content, the amount preferably is in the range of 0.01 to 0.06 wt.%, based on the total amount of the lubricating oil composition.
The zinc dialkyldithiophosphate preferably has an alkyl group of 3 to 18 carbon atoms or an alkylaryl group having an alkyl group of 3 to 18 carbon atoms. It is particularly preferred for the zinc dialkyldithiophosphate to have an alkyl group derived from a secondary alcohol having 3 to 18 carbon atoms or an alkyl group derived from a mixture of a primary alcohol having 3 to 18 carbon atoms and a secondary alcohol having 3 to 18 carbon atoms, because the zinc dialkyldithiophosphate having that alkyl group is particularly effective in wear reduction. A zinc dialkyldithiophosphate derived from a primary alcohol is also excellent in heat resistance. The zinc dithiophosphates can be used singly, but it is preferred to use a mixture mainly comprising a secondary alkyl-type and/or a primary alkyl type.
The lubricating oil composition employed in the method of the present invention may further contain another metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content, based on the total amount of the lubricating oil composition.
The amount of the metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content, based on the total amount of the lubricating oil composition.
The lubricating oil composition employed in the method of the present invention may further contain an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.%
or less, based on the total amount of the lubricating oil composition. In view of having a base number attributable to nitrogen, diarylamine-type oxidation inhibitors are particularly advantageous. On the other hand, however, hindered phenol-type oxidation inhibitors effectively prevent deterioration caused by NOX
oxidation.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octadecyl 3-(3,5-di-t-butyl-4-hyd roxyphenyl)propionate.
Examples of the diarylamine oxidation inhibitors include an alkyldiphenylamine containing a mixture of alkyl groups having 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-a-naphthylamine, phenyl-a-naphthylamine, alkylated a-naphthylamine, and alkylated phenyl-a-naphthylamine.
Each of the hindered phenol compounds and the diarylamine compounds can be used singly or in combination. Other oil soluble oxidation inhibitors can be employed in combination.
The lubricating oil composition employed in the method of the present invention may further contain a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in an amount of 0.25 wt.% or less in terms of the molybdenum content, based on the total amount of the lubricating oil composition.
The molybdenum-containing compound mainly functions as a friction modifier, an oxidation inhibitor or an anti-wear agent in the lubricating oil composition employed in the method of the present invention. In addition, it also improves detergency at a high temperature. The molybdenum-containing compound is preferably in an amount of 10 to 2,500 ppm in terms of the molybdenum content.
Examples of the molybdenum-containing compounds include sulfur-containing molybdenum complex of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine molybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Sulfur-containing molybdenum complex of succinimide is particularly effective in improving the detergency at a high temperature.
The lubricating oil composition employed in the method of the present invention may further contain an alkali metal borate in an amount of 2 wt.% or less, based on the total amount of the lubricating oil composition. The alkali metal borate hydrate is also effective in improving the detergency at a high temperature and in giving a base number. The term "alkali metal borate hydrate" in the present invention means a compound representatively prepared by the method disclosed in U.S. Patent Nos. 3,929,650 and 4,089,790. For example, it can be obtained by the steps of carbonating a neutral alkali metal or alkaline earth metal sulfonate in the presence of an alkali metal hydroxide to prepare a basic sulfonate; and making the basic sulfonate to react with boric acid, to prepare an alkali metal borate in the form of dispersed fine particles. The carbonation reaction is preferably conducted further in the presence of an ashless dispersant such as succinic imide. The alkali metal preferably is potassium or sodium. An example of the alkali metal borate hydrate additive is a suspension comprising a mixture of neutral calcium sulfonate and succinic imide and fine particles of KB305=H20 having sizes of approximately 0.3 pm or less. The potassium can be replaced with sodium. The additive is also preferably used in consideration of water resistance.
The lubricating oil composition employed in the method of the present invention may further contain a viscosity index improver in an amount of 20 wt.% or less, preferably 1 to 20 wt.%, based on the total amount of the lubricating oil composition. Examples of the viscosity index improver include polymer compounds such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. Also employable are dispersant-type viscosity index improvers, which can be obtained by modifying the above polymers so that they can function as dispersants, and multi-functional viscosity index improvers. The viscosity index improvers can be used singly or in combination.
The lubricating oil composition employed in the method of the present invention may further contain various other auxiliary additives. Examples of the auxiliary additives include zinc dithiocarbamate, methylenebis(dibutyldithiocarbamate), an oil-soluble copper compound, a sulfur-containing compound (e.g., sulfurized olefin, sulfurized ester, polysulfide), and an organic amide compound (e.g., oleyl amide). They function as oxidation inhibitors or anti-wear agents. It is also preferred to incorporate metal deactivators such as benzotriazole compounds and thiadiazole compounds. Further, a nonionic surface active agent of polyoxyalkylene such as a copolymer of polyoxyethylenealkylphenyl ether, ethylene oxide and propylene oxide can be added as a rust preventing agent or an demulsifier. It is also possible to incorporate various amines, amides, amine salts or derivatives thereof, and aliphatic acid esters of polyhydric alcohols or their derivatives. They serve as friction modifiers. It is further possible to incorporate various compounds that function as defoaming agents or pour point depressants. Each auxiliary additive is added to the lubricating oil composition employed in the method of the present invention preferably in an amount of 3 wt.% or less, preferably 0.001 to 3 wt.% , based on the total amount of the lubricating oil composition.
Base Oil of Lubricating Viscosity The base oil used in the lubricating oil composition employed in the method of the present invention generally is a mineral or synthetic oil showing a kinematic viscosity of 2 to 50 mm2/s at 100 C. There are no specific conditions with respect to the mineral or synthetic oil, but the base oil has a sulfur content of preferably = 0.1 wt.% or less, more preferably 0.03 wt.% or less, most preferably 0.005 wt.%
or iess.
The mineral base oil is preferably subjected to properly combined treatments.
For example, the mineral lubricant distillate thereof is preferably subjected to treatments such as solvent refining and hydrogenation processing in combination. In the present invention, it is preferred to use a highly hydrogen-refined (hydrocracked) base oil (having, for example, a viscosity index of 100 to 150, an aromatic component content of 5 wt.% or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less). Examples include a high viscosity index-base oil prepared by isomerization or hydrocracking of synthetic wax synthesized from slack wax (crude wax) of mineral oil or natural gas.
It is particularly preferred that the base oil of lubricating viscosity is a mineral oil showing the following characteristics:
evaporation loss (ASTM D-5800): 17 wt.% or less, content of saturated component: 90 wt.% or more, content of aromatic component: 10 wt.% or less, sulfur content: 0.01 wt.% or less, and viscosity index: 120 or more;
or otherwise that the base oil of lubricating viscosity is a mineral oil mixture containing 10 wt.% or more of the above-mentioned mineral oil.
Examples of the synthetic oils (synthetic lubricant base oil) include a poly-a -olefin (copolymer of a-olefin having 3 to 12 carbon atoms), a dialkyl diester (ester derived from an alcohol having 4 to 18 carbon atoms and a dibasic acid such as adipic acid, azelaic acid or sebacic acid) such as dioctyl sebacate, a polyol ester (ester derived from a monobasic acid having 3 to 18 carbon atoms and 1-trimethylolpropane or pentaerythritol), and an alkylbenzene having an alkyl group of 9 to 40 carbon atoms.
Any of the above mineral or synthetic base oils may be used singly, but two or more of the mineral base oils or two or more of the synthetic base oils can be used in combination, if desired. Further, the mineral and synthetic base oils can be used in combination at any ratios, if desired, to prepare the appropriate base oil of lubricating viscosity.
It is preferred to use a major amount of base oil of lubricating viscosity in the lubricating oil composition employed in the method of the present invention. A
major amount of base oil of lubricating viscosity as defined herein comprises wt % or more. Preferred amounts of base oil comprise 40 to 99.9 wt %, preferably greater than 50 to 97 wt %, more preferably 60 to 97 wt % of the lubricating oil composition.
The lubricating oil composition employed in the method of the present invention can be prepared by adding the additives independently or all at once to the base oil. Otherwise, an additive concentrate comprising the additives in high concentrations can be beforehand prepared and then mixed it with a base oil to prepare the lubricating oil composition employed in the method of the present invention.
EXAMPLES
The base oil of lubricating viscosity and the additives used in the below-described Examples and Comparative Example are as follows:
(1) Base oil of lubricating viscosity Solvent refined base oil (A) (kinematic viscosity: 4.9 mm2/s at 100 C, viscosity index: 103, evaporation loss (ASTM D5800): 13 wt.%, sulfur content: 0.19 wt.%, content of saturated component: 70 wt.%) and solvent refined base oil (B) (kinematic viscosity: 10.8 mm2/s at 100 C, viscosity index: 97, evaporation loss (ASTM D5800): 2.3 wt.%, sulfur content: 0.22 wt.%, content of saturated component: 68 wt.%) were mixed in the ratio of 88:12 by weight to use.
(2) Additives Dispersant A: ethylene carbonate-treated succinimide dispersant [N
content: 1.0 wt.%, Cl content: 30 ppm by weight] which was prepared by the steps of:
a) reacting a polybutene having a number average molecular weight of approximately 2,300 and 50% or more of methylvinylidene structure with maleic anhydride according to the thermal process, to produce an intermediate product;
b) reacting the intermediate product with a polyalkylenepolyamine containing 6.5 nitrogen atoms (in one molecule) on average, to prepare succinimide of bis-form; and then c) treating the succinimide of bis-form with ethylene carbonate.
Dispersant B: boron-containing succinimide dispersant [N content: 1.95 wt.%, B content: 0.66 wt.%, Cl content: less than 5 ppm by weight] which was prepared by the steps of:
a) reacting a polybutene having a number average molecular weight of approximately 1,300 and 50% or more of methylvinylidene structure) with maleic anhydride according to the thermal process, to produce an intermediate product;
b) reacting the intermediate product with a polyalkylenepolyamine containing 6.5 nitrogen atoms (in one molecule) on average, to prepare succinimide of bis-form; and then c) treating the succinimide of bis-form with boric acid.
Detergent A: Mannich base calcium phenate (Ca: 2.5 wt.%, N: 1.6 wt.%, S: 0.1 wt.%, TBN: 135 mg=KOH/g).
Detergent B: overbased sulfurized calcium phenate (Ca: 9.25 wt.%, S: 3.4 wt.%, TBN: 255 mg=KOH/g).
Detergent C: overbased calcium sulfonate (Ca: 16.1 wt.%, TBN: 425 mg=KOH/g).
Detergent D: basic calcium sulfonate (Ca: 2.35 wt.%, TBN: 17 mg=KOH/g).
ZnDTP-1: zinc dialkyldithiophosphate (P: 7.2 wt.%, Zn: 7.85 wt.%, S: 14.4 wt.%, starting material: a secondary alcohol having 3 to 6 carbon atoms).
ZnDTP-2: zinc dialkyldithiophosphate (P: 7.3 wt.%, Zn: 8.4 wt.%, S: 14 wt.%, starting material: a primary alcohol having 8 carbon atoms).
Oxidation inhibitor: dialkyldiphenylamine (alkyl group: mixture of C4-alkyl and C8-alkyl groups, N: 4.6 wt.%, TBN: 180 mg=KOH/g).
Mo compound: sulfur-containing molybdenum-succinimide complex (Mo:
5.5 wt.%, S: 0.2 wt.%, N: 1.6 wt.%, TBN: 10 mg=KOH/g).
Alkali metal borate: dispersed fine particles of potassium borate hydrate (K: 8.3 wt.%, B: 6.8 wt.%, S: 0.26 wt.%, TBN: 125 mg=KOH/g).
Viscosity index improver (VII): ethylenepropylene copolymer of non-dispersant type.
Pour point depressant (PPD): polymethacrylic compound.
Example 1 The below-mentioned additives and the base oil of lubricating viscosity were mixed to give the lubricating oil composition employed in the method of the present invention. The lubricating oil composition was SAE viscosity grade 10W30. Also shown below are the contents of each element (Ca, P, N) in the lubricating oil composition, the ratio between the nitrogen content attributable to all the dispersants and that attributable to the detergent A (Mannich base calcium phenate), and the ratio between the metal content attributable to all the detergents and that attributable to the detergent A (Mannich base calcium phenate).
(1) Additives Dispersant A (amount: 3.0 wt.%, content in terms of nitrogen: 0.03 wt.%), Dispersant B (amount: 1.5 wt.%, content in terms of nitrogen: 0.03 wt.%), Detergent A (amount: 0.4 wt.%, content in terms of calcium: 0.01 wt.%, content in terms of nitrogen: 0.006 wt.%), Detergent B (amount: 0.86 wt.%, content in terms of calcium: 0.08 wt.%), Detergent C (amount: 0.87 wt.%, content in terms of calcium: 0.14 wt.%), Detergent D (amount: 0.43 wt.%, content in terms of calcium: 0.01 wt.%), ZnDTP-1 (amount: 0.97 wt.%, content in terms of phosphorus: 0.07 wt.%), ZnDTP-2 (amount: 0.41 wt.%, content in terms of phosphorus: 0.03 wt.%), Oxidation inhibitor (amount: 0.2 wt.%), Mo compound (amount: 0.15 wt.%, content in terms of molybdenum: 83 ppm by weight), Alkali metal borate (amount: 0.25 wt.%), Viscosity index improver (VII, amount: 6.3 wt.%), and Pour point depressant (PPD, amount: 0.3 wt.%).
(2) Base oil of lubricating viscosity (amount: residual amount) (3) Content of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.24 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.08 wt.%
(4) Ratio of the nitrogen content attributable to all the dispersants to that attributable to the detergent A (Mannich base calcium phenate): 1:0.1 (5) Ratio of the metal content attributable to all the detergents in the composition to that attributable to the detergent A (Mannich base calcium phenate): 1:0.04 Example 2 The procedures of Example 1 were repeated except for changing the amount of the detergent A (Mannich base calcium phenate) into 1.16 wt.% (content in terms of calcium: 0.03 wt.%, content in terms of nitrogen: 0.018 wt.%) and for changing the residual amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%. The prepared lubricating oil composition was SAE viscosity grade 10W30. Shown below are the contents of each element (Ca, P, N) in the lubricating oil composition, a ratio between the nitrogen content attributable to all the dispersants and that attributable to the detergent A (Mannich base calcium phenate), and a ratio between the metal content attributable to all the detergents and that attributable to the detergent A
(Mannich base calcium phenate).
(1) Contents of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.26 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.09 wt.%
(2) Ratio of the nitrogen content attributable to all the dispersants to that attributable to the detergent A (Mannich base calcium phenate): 1:0.3 (3) Ratio of the metal content attributable to all the detergents in the lubricating oil composition to that attributable to the detergent A (Mannich base calcium phenate): 1:0.12 Comparative Example A
Comparative Example A was prepared according to the procedures of Example 1 except for not adding the detergent A (Mannich base calcium phenate) and for changing the amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%. The prepared lubricating oil composition was SAE viscosity grade 10W30. The contents of each element (Ca, P, N) in the lubricating oil composition are shown below.
(1) Contents of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.23 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.07 wt.%
Evaluation of Compatibility With Acrylic Rubber Sealant According to the affinity test for sealing rubber (CEC-L-39-T-96), compatibility with acrylic rubber was evaluated in the following manner. A piece of RE2-99 (acrylic rubber) was immersed in the lubricating oil composition to be tested at 150 C for 7 days, and then the degree of deterioration of the acrylic rubber piece was evaluated. The results are set forth in Table 1. In Table 1, the pass limits specified in JASO (Japanese Automobile Standard Organization) M355-2005 are also shown.
Table 1.
Pass Limit Example 1 Example 2 Comparative Example A
Volume -7 to +5 +2 0 +2 change(%) Hardness -5 to +8 +3 +4 +3 change Tensile strength -15 to +18 +2 +2 -4 change (%) Elongation -35 to +10 -23 -19 -35 change(%) The above results shown in Table 1 indicate that both the lubricating oil compositions of the present invention (Examples 1 and 2) and that for Comparative Example A satisfy the JASO standards. It is also shown that the lubricating oil compositions of the present invention were remarkably improved in the elongation change, as compared with the lubricating oil composition for comparative example.
CaOH CaOH CaOH
N
R n R
The amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of 0.001 to 0.4 wt.% in terms of the metal content or 0.002 to 0.1 wt.%
in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
The metal-containing detergent of an alkali metal (e.g., sodium, potassium) or alkaline earth metal (e.g., calcium, barium, magnesium) salt of alkylphenol derivative having a Mannich base structure, is generally prepared by the steps of:
synthesizing an intermediate having aminomethylated phenol ring by Mannich reaction from alkylphenol, formaldehyde, amine or an amine compound; and neutralizing the synthesized intermediate with a base such as calcium hydroxide to covert it into a metal salt. Examples include the compound of the above formula having the following characteristics:
Ca content: 2.5 wt.%, N content: 1.6 wt.%, total base number: 135 mg=KOH/g, and base number attributable to basic nitrogen: approximately 50% of the total base number.
The ratio of the nitrogen-containing ashless dispersant to the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of from 1:0.005 to 1:2, preferably 1:0.01 to 1:0.3, in terms of the nitrogen content.
The lubricating oil composition employed in the method of the present invention will contain a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
The amount of the phosphorus-containing organic compound is in the range of 0.001 to 0.5 wt.%, preferably 0.01 to 0.2 wt.%, in terms of the phosphorus content, based on the total amount of the lubricating oil composition.
Examples of the phosphorus-containing organic compounds include zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters in which each ester is generally derived from the corresponding acid and an alkylalcohol having 3 to 18 carbon atoms or an alkylarylalcohol having an alkyl group of 3 to 18 carbon atoms. If a zinc dihydrocarbyldithiophosphate (zinc dialkyldithiophosphate) is added, the amount of the additive is preferably in the range of 0.01 to 0.1 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition. From the viewpoint of reducing the phosphorus content and the sulfur content, the amount preferably is in the range of 0.01 to 0.06 wt.%, based on the total amount of the lubricating oil composition.
The zinc dialkyldithiophosphate preferably has an alkyl group of 3 to 18 carbon atoms or an alkylaryl group having an alkyl group of 3 to 18 carbon atoms. It is particularly preferred for the zinc dialkyldithiophosphate to have an alkyl group derived from a secondary alcohol having 3 to 18 carbon atoms or an alkyl group derived from a mixture of a primary alcohol having 3 to 18 carbon atoms and a secondary alcohol having 3 to 18 carbon atoms, because the zinc dialkyldithiophosphate having that alkyl group is particularly effective in wear reduction. A zinc dialkyldithiophosphate derived from a primary alcohol is also excellent in heat resistance. The zinc dithiophosphates can be used singly, but it is preferred to use a mixture mainly comprising a secondary alkyl-type and/or a primary alkyl type.
The lubricating oil composition employed in the method of the present invention may further contain another metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content, based on the total amount of the lubricating oil composition.
The amount of the metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content, based on the total amount of the lubricating oil composition.
The lubricating oil composition employed in the method of the present invention may further contain an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.%
or less, based on the total amount of the lubricating oil composition. In view of having a base number attributable to nitrogen, diarylamine-type oxidation inhibitors are particularly advantageous. On the other hand, however, hindered phenol-type oxidation inhibitors effectively prevent deterioration caused by NOX
oxidation.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octadecyl 3-(3,5-di-t-butyl-4-hyd roxyphenyl)propionate.
Examples of the diarylamine oxidation inhibitors include an alkyldiphenylamine containing a mixture of alkyl groups having 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-a-naphthylamine, phenyl-a-naphthylamine, alkylated a-naphthylamine, and alkylated phenyl-a-naphthylamine.
Each of the hindered phenol compounds and the diarylamine compounds can be used singly or in combination. Other oil soluble oxidation inhibitors can be employed in combination.
The lubricating oil composition employed in the method of the present invention may further contain a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in an amount of 0.25 wt.% or less in terms of the molybdenum content, based on the total amount of the lubricating oil composition.
The molybdenum-containing compound mainly functions as a friction modifier, an oxidation inhibitor or an anti-wear agent in the lubricating oil composition employed in the method of the present invention. In addition, it also improves detergency at a high temperature. The molybdenum-containing compound is preferably in an amount of 10 to 2,500 ppm in terms of the molybdenum content.
Examples of the molybdenum-containing compounds include sulfur-containing molybdenum complex of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine molybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Sulfur-containing molybdenum complex of succinimide is particularly effective in improving the detergency at a high temperature.
The lubricating oil composition employed in the method of the present invention may further contain an alkali metal borate in an amount of 2 wt.% or less, based on the total amount of the lubricating oil composition. The alkali metal borate hydrate is also effective in improving the detergency at a high temperature and in giving a base number. The term "alkali metal borate hydrate" in the present invention means a compound representatively prepared by the method disclosed in U.S. Patent Nos. 3,929,650 and 4,089,790. For example, it can be obtained by the steps of carbonating a neutral alkali metal or alkaline earth metal sulfonate in the presence of an alkali metal hydroxide to prepare a basic sulfonate; and making the basic sulfonate to react with boric acid, to prepare an alkali metal borate in the form of dispersed fine particles. The carbonation reaction is preferably conducted further in the presence of an ashless dispersant such as succinic imide. The alkali metal preferably is potassium or sodium. An example of the alkali metal borate hydrate additive is a suspension comprising a mixture of neutral calcium sulfonate and succinic imide and fine particles of KB305=H20 having sizes of approximately 0.3 pm or less. The potassium can be replaced with sodium. The additive is also preferably used in consideration of water resistance.
The lubricating oil composition employed in the method of the present invention may further contain a viscosity index improver in an amount of 20 wt.% or less, preferably 1 to 20 wt.%, based on the total amount of the lubricating oil composition. Examples of the viscosity index improver include polymer compounds such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. Also employable are dispersant-type viscosity index improvers, which can be obtained by modifying the above polymers so that they can function as dispersants, and multi-functional viscosity index improvers. The viscosity index improvers can be used singly or in combination.
The lubricating oil composition employed in the method of the present invention may further contain various other auxiliary additives. Examples of the auxiliary additives include zinc dithiocarbamate, methylenebis(dibutyldithiocarbamate), an oil-soluble copper compound, a sulfur-containing compound (e.g., sulfurized olefin, sulfurized ester, polysulfide), and an organic amide compound (e.g., oleyl amide). They function as oxidation inhibitors or anti-wear agents. It is also preferred to incorporate metal deactivators such as benzotriazole compounds and thiadiazole compounds. Further, a nonionic surface active agent of polyoxyalkylene such as a copolymer of polyoxyethylenealkylphenyl ether, ethylene oxide and propylene oxide can be added as a rust preventing agent or an demulsifier. It is also possible to incorporate various amines, amides, amine salts or derivatives thereof, and aliphatic acid esters of polyhydric alcohols or their derivatives. They serve as friction modifiers. It is further possible to incorporate various compounds that function as defoaming agents or pour point depressants. Each auxiliary additive is added to the lubricating oil composition employed in the method of the present invention preferably in an amount of 3 wt.% or less, preferably 0.001 to 3 wt.% , based on the total amount of the lubricating oil composition.
Base Oil of Lubricating Viscosity The base oil used in the lubricating oil composition employed in the method of the present invention generally is a mineral or synthetic oil showing a kinematic viscosity of 2 to 50 mm2/s at 100 C. There are no specific conditions with respect to the mineral or synthetic oil, but the base oil has a sulfur content of preferably = 0.1 wt.% or less, more preferably 0.03 wt.% or less, most preferably 0.005 wt.%
or iess.
The mineral base oil is preferably subjected to properly combined treatments.
For example, the mineral lubricant distillate thereof is preferably subjected to treatments such as solvent refining and hydrogenation processing in combination. In the present invention, it is preferred to use a highly hydrogen-refined (hydrocracked) base oil (having, for example, a viscosity index of 100 to 150, an aromatic component content of 5 wt.% or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less). Examples include a high viscosity index-base oil prepared by isomerization or hydrocracking of synthetic wax synthesized from slack wax (crude wax) of mineral oil or natural gas.
It is particularly preferred that the base oil of lubricating viscosity is a mineral oil showing the following characteristics:
evaporation loss (ASTM D-5800): 17 wt.% or less, content of saturated component: 90 wt.% or more, content of aromatic component: 10 wt.% or less, sulfur content: 0.01 wt.% or less, and viscosity index: 120 or more;
or otherwise that the base oil of lubricating viscosity is a mineral oil mixture containing 10 wt.% or more of the above-mentioned mineral oil.
Examples of the synthetic oils (synthetic lubricant base oil) include a poly-a -olefin (copolymer of a-olefin having 3 to 12 carbon atoms), a dialkyl diester (ester derived from an alcohol having 4 to 18 carbon atoms and a dibasic acid such as adipic acid, azelaic acid or sebacic acid) such as dioctyl sebacate, a polyol ester (ester derived from a monobasic acid having 3 to 18 carbon atoms and 1-trimethylolpropane or pentaerythritol), and an alkylbenzene having an alkyl group of 9 to 40 carbon atoms.
Any of the above mineral or synthetic base oils may be used singly, but two or more of the mineral base oils or two or more of the synthetic base oils can be used in combination, if desired. Further, the mineral and synthetic base oils can be used in combination at any ratios, if desired, to prepare the appropriate base oil of lubricating viscosity.
It is preferred to use a major amount of base oil of lubricating viscosity in the lubricating oil composition employed in the method of the present invention. A
major amount of base oil of lubricating viscosity as defined herein comprises wt % or more. Preferred amounts of base oil comprise 40 to 99.9 wt %, preferably greater than 50 to 97 wt %, more preferably 60 to 97 wt % of the lubricating oil composition.
The lubricating oil composition employed in the method of the present invention can be prepared by adding the additives independently or all at once to the base oil. Otherwise, an additive concentrate comprising the additives in high concentrations can be beforehand prepared and then mixed it with a base oil to prepare the lubricating oil composition employed in the method of the present invention.
EXAMPLES
The base oil of lubricating viscosity and the additives used in the below-described Examples and Comparative Example are as follows:
(1) Base oil of lubricating viscosity Solvent refined base oil (A) (kinematic viscosity: 4.9 mm2/s at 100 C, viscosity index: 103, evaporation loss (ASTM D5800): 13 wt.%, sulfur content: 0.19 wt.%, content of saturated component: 70 wt.%) and solvent refined base oil (B) (kinematic viscosity: 10.8 mm2/s at 100 C, viscosity index: 97, evaporation loss (ASTM D5800): 2.3 wt.%, sulfur content: 0.22 wt.%, content of saturated component: 68 wt.%) were mixed in the ratio of 88:12 by weight to use.
(2) Additives Dispersant A: ethylene carbonate-treated succinimide dispersant [N
content: 1.0 wt.%, Cl content: 30 ppm by weight] which was prepared by the steps of:
a) reacting a polybutene having a number average molecular weight of approximately 2,300 and 50% or more of methylvinylidene structure with maleic anhydride according to the thermal process, to produce an intermediate product;
b) reacting the intermediate product with a polyalkylenepolyamine containing 6.5 nitrogen atoms (in one molecule) on average, to prepare succinimide of bis-form; and then c) treating the succinimide of bis-form with ethylene carbonate.
Dispersant B: boron-containing succinimide dispersant [N content: 1.95 wt.%, B content: 0.66 wt.%, Cl content: less than 5 ppm by weight] which was prepared by the steps of:
a) reacting a polybutene having a number average molecular weight of approximately 1,300 and 50% or more of methylvinylidene structure) with maleic anhydride according to the thermal process, to produce an intermediate product;
b) reacting the intermediate product with a polyalkylenepolyamine containing 6.5 nitrogen atoms (in one molecule) on average, to prepare succinimide of bis-form; and then c) treating the succinimide of bis-form with boric acid.
Detergent A: Mannich base calcium phenate (Ca: 2.5 wt.%, N: 1.6 wt.%, S: 0.1 wt.%, TBN: 135 mg=KOH/g).
Detergent B: overbased sulfurized calcium phenate (Ca: 9.25 wt.%, S: 3.4 wt.%, TBN: 255 mg=KOH/g).
Detergent C: overbased calcium sulfonate (Ca: 16.1 wt.%, TBN: 425 mg=KOH/g).
Detergent D: basic calcium sulfonate (Ca: 2.35 wt.%, TBN: 17 mg=KOH/g).
ZnDTP-1: zinc dialkyldithiophosphate (P: 7.2 wt.%, Zn: 7.85 wt.%, S: 14.4 wt.%, starting material: a secondary alcohol having 3 to 6 carbon atoms).
ZnDTP-2: zinc dialkyldithiophosphate (P: 7.3 wt.%, Zn: 8.4 wt.%, S: 14 wt.%, starting material: a primary alcohol having 8 carbon atoms).
Oxidation inhibitor: dialkyldiphenylamine (alkyl group: mixture of C4-alkyl and C8-alkyl groups, N: 4.6 wt.%, TBN: 180 mg=KOH/g).
Mo compound: sulfur-containing molybdenum-succinimide complex (Mo:
5.5 wt.%, S: 0.2 wt.%, N: 1.6 wt.%, TBN: 10 mg=KOH/g).
Alkali metal borate: dispersed fine particles of potassium borate hydrate (K: 8.3 wt.%, B: 6.8 wt.%, S: 0.26 wt.%, TBN: 125 mg=KOH/g).
Viscosity index improver (VII): ethylenepropylene copolymer of non-dispersant type.
Pour point depressant (PPD): polymethacrylic compound.
Example 1 The below-mentioned additives and the base oil of lubricating viscosity were mixed to give the lubricating oil composition employed in the method of the present invention. The lubricating oil composition was SAE viscosity grade 10W30. Also shown below are the contents of each element (Ca, P, N) in the lubricating oil composition, the ratio between the nitrogen content attributable to all the dispersants and that attributable to the detergent A (Mannich base calcium phenate), and the ratio between the metal content attributable to all the detergents and that attributable to the detergent A (Mannich base calcium phenate).
(1) Additives Dispersant A (amount: 3.0 wt.%, content in terms of nitrogen: 0.03 wt.%), Dispersant B (amount: 1.5 wt.%, content in terms of nitrogen: 0.03 wt.%), Detergent A (amount: 0.4 wt.%, content in terms of calcium: 0.01 wt.%, content in terms of nitrogen: 0.006 wt.%), Detergent B (amount: 0.86 wt.%, content in terms of calcium: 0.08 wt.%), Detergent C (amount: 0.87 wt.%, content in terms of calcium: 0.14 wt.%), Detergent D (amount: 0.43 wt.%, content in terms of calcium: 0.01 wt.%), ZnDTP-1 (amount: 0.97 wt.%, content in terms of phosphorus: 0.07 wt.%), ZnDTP-2 (amount: 0.41 wt.%, content in terms of phosphorus: 0.03 wt.%), Oxidation inhibitor (amount: 0.2 wt.%), Mo compound (amount: 0.15 wt.%, content in terms of molybdenum: 83 ppm by weight), Alkali metal borate (amount: 0.25 wt.%), Viscosity index improver (VII, amount: 6.3 wt.%), and Pour point depressant (PPD, amount: 0.3 wt.%).
(2) Base oil of lubricating viscosity (amount: residual amount) (3) Content of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.24 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.08 wt.%
(4) Ratio of the nitrogen content attributable to all the dispersants to that attributable to the detergent A (Mannich base calcium phenate): 1:0.1 (5) Ratio of the metal content attributable to all the detergents in the composition to that attributable to the detergent A (Mannich base calcium phenate): 1:0.04 Example 2 The procedures of Example 1 were repeated except for changing the amount of the detergent A (Mannich base calcium phenate) into 1.16 wt.% (content in terms of calcium: 0.03 wt.%, content in terms of nitrogen: 0.018 wt.%) and for changing the residual amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%. The prepared lubricating oil composition was SAE viscosity grade 10W30. Shown below are the contents of each element (Ca, P, N) in the lubricating oil composition, a ratio between the nitrogen content attributable to all the dispersants and that attributable to the detergent A (Mannich base calcium phenate), and a ratio between the metal content attributable to all the detergents and that attributable to the detergent A
(Mannich base calcium phenate).
(1) Contents of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.26 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.09 wt.%
(2) Ratio of the nitrogen content attributable to all the dispersants to that attributable to the detergent A (Mannich base calcium phenate): 1:0.3 (3) Ratio of the metal content attributable to all the detergents in the lubricating oil composition to that attributable to the detergent A (Mannich base calcium phenate): 1:0.12 Comparative Example A
Comparative Example A was prepared according to the procedures of Example 1 except for not adding the detergent A (Mannich base calcium phenate) and for changing the amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%. The prepared lubricating oil composition was SAE viscosity grade 10W30. The contents of each element (Ca, P, N) in the lubricating oil composition are shown below.
(1) Contents of each element (Ca, P, N) in the lubricating oil composition Calcium (Ca): 0.23 wt.%, Phosphorus (P): 0.10 wt.%, Nitrogen (N): 0.07 wt.%
Evaluation of Compatibility With Acrylic Rubber Sealant According to the affinity test for sealing rubber (CEC-L-39-T-96), compatibility with acrylic rubber was evaluated in the following manner. A piece of RE2-99 (acrylic rubber) was immersed in the lubricating oil composition to be tested at 150 C for 7 days, and then the degree of deterioration of the acrylic rubber piece was evaluated. The results are set forth in Table 1. In Table 1, the pass limits specified in JASO (Japanese Automobile Standard Organization) M355-2005 are also shown.
Table 1.
Pass Limit Example 1 Example 2 Comparative Example A
Volume -7 to +5 +2 0 +2 change(%) Hardness -5 to +8 +3 +4 +3 change Tensile strength -15 to +18 +2 +2 -4 change (%) Elongation -35 to +10 -23 -19 -35 change(%) The above results shown in Table 1 indicate that both the lubricating oil compositions of the present invention (Examples 1 and 2) and that for Comparative Example A satisfy the JASO standards. It is also shown that the lubricating oil compositions of the present invention were remarkably improved in the elongation change, as compared with the lubricating oil composition for comparative example.
Claims (15)
1. A method of improving the acrylic rubber sealant compatibility in an internal combustion engine, said method comprising contacting the acrylic rubber sealant in the internal combustion engine and operating the internal combustion engine with a lubricating oil composition comprising:
a) a major amount of a base oil of lubricating viscosity, b) a nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.% in terms of the nitrogen content, based on the total amount of the lubricating oil composition, c) a metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure in an amount of 0.001 to 0.4 wt.% in terms of the metal content, based on the total amount of the lubricating oil composition, and d) a phosphorus-containing organic compound in an amount of 0.001 to 0.5 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition, wherein the ratio of components b) to c) is in the range of from 1:0.005 to 1:2 in terms of the nitrogen content.
a) a major amount of a base oil of lubricating viscosity, b) a nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.% in terms of the nitrogen content, based on the total amount of the lubricating oil composition, c) a metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure in an amount of 0.001 to 0.4 wt.% in terms of the metal content, based on the total amount of the lubricating oil composition, and d) a phosphorus-containing organic compound in an amount of 0.001 to 0.5 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition, wherein the ratio of components b) to c) is in the range of from 1:0.005 to 1:2 in terms of the nitrogen content.
2. The method according to Claim 1, wherein the nitrogen-containing ashless dispersant is an alkenyl- or alkyl-succinic imide or a derivative thereof.
3. The method according to Claim 1, wherein the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is represented by the following formula:
wherein R is an alkyl group having 8 to 30 carbon atoms, and n is 0 or a positive integer.
wherein R is an alkyl group having 8 to 30 carbon atoms, and n is 0 or a positive integer.
4. The method according to Claim 1, wherein the phosphorus-containing organic compound is selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
5. The method according to Claim 1, wherein the amount of the nitrogen-containing ashless dispersant is in the range of 0.01 to 0.1 wt.% in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
6. The method according to Claim 1, wherein the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of 0.002 to 0.1 wt.% in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
7. The method according to Claim 1, wherein the amount of the phosphorus-containing organic compound is in the range of 0.01 to 0.2 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition.
8. The method according to Claim 1, further comprising a metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content, based on the total amount of the lubricating oil composition.
9. The method according to Claim 8, wherein the amount of metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates and the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content.
10. The method according to Claim 1, further comprising a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in amount of 0.25 wt.% or less in terms of the molybdenum content, based on the total amount of the lubricating oil composition.
11. The method according to Claim 1, further comprising an alkali metal borate in an amount of 2 wt.% or less, based on the total amount of the lubricating oil composition.
12. The method according to Claim 1, further comprising an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less, based on the total amount of the lubricating oil composition.
13. The method according to Claim 1, wherein the base oil contains 10 wt.% or more of a mineral oil showing the following characteristics:
- 17 wt.% or less evaporation loss according to ASTM
D-5800, - 90 wt.% or more saturated content, - 10 wt.% or less, aromatic component, - 0.01 wt.% or less, sulfur content, and - 120 or more viscosity index.
- 17 wt.% or less evaporation loss according to ASTM
D-5800, - 90 wt.% or more saturated content, - 10 wt.% or less, aromatic component, - 0.01 wt.% or less, sulfur content, and - 120 or more viscosity index.
14. The method according to Claim 1, wherein the lubricating oil composition is a SAE viscosity grade selected from the group consisting of 0W20, 0W30, 5W20, 5W30 and 10W30.
15. The method according to Claim 14, wherein the lubricating oil composition is a SAE viscosity grade selected from the group consisting of 10W30.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005375974A JP4955998B2 (en) | 2005-12-27 | 2005-12-27 | Lubricating oil composition |
| JP2005-375974 | 2005-12-27 |
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| US (1) | US20070184992A1 (en) |
| EP (1) | EP1803797B1 (en) |
| JP (1) | JP4955998B2 (en) |
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| US20080128184A1 (en) * | 2006-11-30 | 2008-06-05 | Loper John T | Lubricating oil compositions having improved corrosion and seal protection properties |
| US20090247438A1 (en) * | 2008-03-31 | 2009-10-01 | Exxonmobil Research And Engineering Company | Hydraulic oil formulation and method to improve seal swell |
| US20100081591A1 (en) * | 2008-09-30 | 2010-04-01 | Chevron Oronite Company Llc | Lubricating oil compositions |
| US8993496B2 (en) | 2010-03-31 | 2015-03-31 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
| US8901050B2 (en) | 2010-03-31 | 2014-12-02 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
| US8716202B2 (en) | 2010-12-14 | 2014-05-06 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
| SG11201401684QA (en) * | 2011-12-16 | 2014-05-29 | Chevron Oronite Co | Diesel engine oils |
| EP3369802B1 (en) * | 2017-03-01 | 2019-07-10 | Infineum International Limited | Improvements in and relating to lubricating compositions |
| US12146115B2 (en) | 2022-12-20 | 2024-11-19 | Afton Chemical Corporation | Low ash lubricating compositions for controlling steel corrosion |
| US12195695B2 (en) | 2023-05-10 | 2025-01-14 | Afton Chemical Corporation | Lubricating oil compositions for improving low-speed pre-ignition |
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| US4713189A (en) * | 1986-08-20 | 1987-12-15 | Texaco, Inc. | Precoupled mono-succinimide lubricating oil dispersants and viton seal additives |
| US5370805A (en) * | 1993-11-18 | 1994-12-06 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Chlorine-free diesel engine lubricating composition |
| EP0684298A3 (en) * | 1994-05-23 | 1996-04-03 | Lubrizol Corp | Compositions for extending seal life, and lubricants and functional fluids containing the same. |
| FR2762848B1 (en) * | 1997-05-05 | 2000-02-04 | Chevron Res & Tech | USE OF BORATE COMPOUNDS FOR IMPROVING THE COMPATIBILITY OF LUBRICATING OILS WITH FLUOROCARBON ELASTOMERS |
| JP3261340B2 (en) * | 1997-05-30 | 2002-02-25 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| JP4107702B2 (en) * | 1997-12-19 | 2008-06-25 | 昭和シェル石油株式会社 | Lubricating oil composition with excellent sealing material compatibility |
| JP3722472B2 (en) * | 2000-06-02 | 2005-11-30 | シェブロンテキサコジャパン株式会社 | Lubricating oil composition |
| US6569818B2 (en) * | 2000-06-02 | 2003-05-27 | Chevron Oronite Company, Llc | Lubricating oil composition |
| EP1439217B1 (en) * | 2001-10-12 | 2012-06-20 | Nippon Oil Corporation | Lubricating oil composition for internal combustion engine |
| JP4066132B2 (en) * | 2001-10-15 | 2008-03-26 | 株式会社Ａｄｅｋａ | Lubricant and lubricating composition |
| JP4011967B2 (en) * | 2002-05-07 | 2007-11-21 | シェブロンジャパン株式会社 | Lubricating oil composition |
| CN100500817C (en) * | 2002-08-27 | 2009-06-17 | 新日本石油株式会社 | Lubricating oil compositions |
| US7285516B2 (en) * | 2002-11-25 | 2007-10-23 | The Lubrizol Corporation | Additive formulation for lubricating oils |
| US20040171501A1 (en) * | 2003-02-27 | 2004-09-02 | Leeuwen Jeroen Van | Method for improving elastomer compatibility |
| US7985592B2 (en) * | 2004-02-13 | 2011-07-26 | Chevron Oronite Company Llc | High throughput screening methods for lubricating oil compositions |
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| JP2007177052A (en) | 2007-07-12 |
| EP1803797A3 (en) | 2010-07-28 |
| JP4955998B2 (en) | 2012-06-20 |
| CA2572041C (en) | 2015-02-17 |
| EP1803797B1 (en) | 2014-12-03 |
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| SG133568A1 (en) | 2007-07-30 |
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