EP1896556B1 - Oxidative stable oil formulation - Google Patents
Oxidative stable oil formulation Download PDFInfo
- Publication number
- EP1896556B1 EP1896556B1 EP06777414.1A EP06777414A EP1896556B1 EP 1896556 B1 EP1896556 B1 EP 1896556B1 EP 06777414 A EP06777414 A EP 06777414A EP 1896556 B1 EP1896556 B1 EP 1896556B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oil
- oil
- formulation according
- formulation
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 98
- 238000009472 formulation Methods 0.000 title claims description 54
- 230000001590 oxidative effect Effects 0.000 title description 8
- 239000003921 oil Substances 0.000 claims description 78
- 239000002199 base oil Substances 0.000 claims description 76
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 21
- 239000011707 mineral Substances 0.000 claims description 21
- 235000006708 antioxidants Nutrition 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007866 anti-wear additive Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 150000008116 organic polysulfides Chemical group 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000654 additive Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 11
- 239000010802 sludge Substances 0.000 description 10
- -1 polyol ester Chemical class 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 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 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- ZQMPWXFHAUDENN-UHFFFAOYSA-N 1,2-bis[(2-methylphenyl)amino]ethane Natural products CC1=CC=CC=C1NCCNC1=CC=CC=C1C ZQMPWXFHAUDENN-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- GAYUSSOCODCSNF-UHFFFAOYSA-N 1-(dodecyldisulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSCCCCCCCCCCCC GAYUSSOCODCSNF-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- SKHBJDDIGYYYMJ-UHFFFAOYSA-N 2,6-ditert-butyl-6-methylcyclohexa-1,3-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C(C)(C(C)(C)C)CC=C1 SKHBJDDIGYYYMJ-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 210000002741 palatine tonsil Anatomy 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- JUHXTONDLXIGGK-UHFFFAOYSA-N 1-n,4-n-bis(5-methylheptan-3-yl)benzene-1,4-diamine Chemical compound CCC(C)CC(CC)NC1=CC=C(NC(CC)CC(C)CC)C=C1 JUHXTONDLXIGGK-UHFFFAOYSA-N 0.000 description 1
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 description 1
- BJLNXEQCTFMBTH-UHFFFAOYSA-N 1-n,4-n-di(butan-2-yl)-1-n,4-n-dimethylbenzene-1,4-diamine Chemical compound CCC(C)N(C)C1=CC=C(N(C)C(C)CC)C=C1 BJLNXEQCTFMBTH-UHFFFAOYSA-N 0.000 description 1
- APTGHASZJUAUCP-UHFFFAOYSA-N 1-n,4-n-di(octan-2-yl)benzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(NC(C)CCCCCC)C=C1 APTGHASZJUAUCP-UHFFFAOYSA-N 0.000 description 1
- PWNBRRGFUVBTQG-UHFFFAOYSA-N 1-n,4-n-di(propan-2-yl)benzene-1,4-diamine Chemical compound CC(C)NC1=CC=C(NC(C)C)C=C1 PWNBRRGFUVBTQG-UHFFFAOYSA-N 0.000 description 1
- AIMXDOGPMWDCDF-UHFFFAOYSA-N 1-n,4-n-dicyclohexylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1CCCCC1 AIMXDOGPMWDCDF-UHFFFAOYSA-N 0.000 description 1
- GFVSLJXVNAYUJE-UHFFFAOYSA-N 10-prop-2-enylphenothiazine Chemical compound C1=CC=C2N(CC=C)C3=CC=CC=C3SC2=C1 GFVSLJXVNAYUJE-UHFFFAOYSA-N 0.000 description 1
- LXWZXEJDKYWBOW-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O LXWZXEJDKYWBOW-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- RWYIKYWUOWLWHZ-UHFFFAOYSA-N 3,3-dimethyl-2,4-dihydro-1,4-benzothiazine Chemical compound C1=CC=C2NC(C)(C)CSC2=C1 RWYIKYWUOWLWHZ-UHFFFAOYSA-N 0.000 description 1
- VZXJHQBFMJESBV-UHFFFAOYSA-N 3,7-bis(2,4,4-trimethylpentan-2-yl)-10h-phenothiazine Chemical compound C1=C(C(C)(C)CC(C)(C)C)C=C2SC3=CC(C(C)(C)CC(C)(C)C)=CC=C3NC2=C1 VZXJHQBFMJESBV-UHFFFAOYSA-N 0.000 description 1
- HLFQEOHPFTVZLO-UHFFFAOYSA-N 3-methyl-2-(5-methyl-2H-triazol-4-yl)-N,N-dioctylaniline Chemical compound C(CCCCCCC)N(CCCCCCCC)C=1C(=C(C=CC=1)C)C=1N=NNC=1C HLFQEOHPFTVZLO-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- KCWYKOQNHLULEK-UHFFFAOYSA-N 4,5-diethyl-2h-benzotriazole Chemical compound CCC1=CC=C2NN=NC2=C1CC KCWYKOQNHLULEK-UHFFFAOYSA-N 0.000 description 1
- HXICLUNGKDYXRL-UHFFFAOYSA-N 4,5-dimethyl-2h-benzotriazole Chemical compound CC1=CC=C2NN=NC2=C1C HXICLUNGKDYXRL-UHFFFAOYSA-N 0.000 description 1
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 1
- VAMBUGIXOVLJEA-UHFFFAOYSA-N 4-(butylamino)phenol Chemical compound CCCCNC1=CC=C(O)C=C1 VAMBUGIXOVLJEA-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- KZNDXCVEWRZEEU-UHFFFAOYSA-N 4-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1CCCCC1 KZNDXCVEWRZEEU-UHFFFAOYSA-N 0.000 description 1
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- URFSURIOYABYBY-UHFFFAOYSA-N 5-ethyl-4-methyl-2h-benzotriazole Chemical compound CCC1=CC=C2NN=NC2=C1C URFSURIOYABYBY-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical class C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
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- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
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- 229920002367 Polyisobutene Polymers 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
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- KESXDDATSRRGAH-UHFFFAOYSA-N n-(4-hydroxyphenyl)butanamide Chemical compound CCCC(=O)NC1=CC=C(O)C=C1 KESXDDATSRRGAH-UHFFFAOYSA-N 0.000 description 1
- JVKWTDRHWOSRFT-UHFFFAOYSA-N n-(4-hydroxyphenyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 JVKWTDRHWOSRFT-UHFFFAOYSA-N 0.000 description 1
- VQLURHRLTDWRLX-UHFFFAOYSA-N n-(4-hydroxyphenyl)nonanamide Chemical compound CCCCCCCCC(=O)NC1=CC=C(O)C=C1 VQLURHRLTDWRLX-UHFFFAOYSA-N 0.000 description 1
- YASWBJXTHOXPGK-UHFFFAOYSA-N n-(4-hydroxyphenyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 YASWBJXTHOXPGK-UHFFFAOYSA-N 0.000 description 1
- CVVFFUKULYKOJR-UHFFFAOYSA-N n-phenyl-4-propan-2-yloxyaniline Chemical compound C1=CC(OC(C)C)=CC=C1NC1=CC=CC=C1 CVVFFUKULYKOJR-UHFFFAOYSA-N 0.000 description 1
- NYLGUNUDTDWXQE-UHFFFAOYSA-N n-phenyl-n-prop-2-enylaniline Chemical compound C=1C=CC=CC=1N(CC=C)C1=CC=CC=C1 NYLGUNUDTDWXQE-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 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
- 238000013021 overheating Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- 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
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/083—Dibenzyl sulfide
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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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
- C10N2030/64—Environmental friendly compositions
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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
- C10N2040/14—Electric or magnetic purposes
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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
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
-
- 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
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the invention is related to an oxidation stable oil formulation comprising a base oil composition and additives.
- US-A-6790386 describes a dielectric fluid comprising an iso-paraffin base oil and additives.
- the iso-paraffin base oil is prepared by hydrotreating, hydroisomerisation and hydrogenation of a paraffinic vacuum feedstock.
- US-A-6214776 describes a formulation comprising a paraffinic base oil and an additive package containing a hindered phenol antioxidant and a metal deactivator, for use as load tap changer or transformer oil.
- base oils having a kinematic viscosity at 40 °C of between 5 and 20 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
- US-A-5241003 discloses a combination of a sulfur-containing antiwear additive and a carboxylic derivative dispersant for use as additive package for lubricants.
- US-A-5773391 describes a composition comprising a polyol ester base oil, an aliphatic monocarboxylic acid mixture, and an additive package comprising an antioxidant and a metal deactivator.
- the document further discloses phosphorodithionates as antiwear additives.
- WO-A-02070629 describes a process to make isoparaffinic base oils from a wax as made in a Fischer-Tropsch process.
- base oils having a kinematic viscosity at 100 °C of between 2 and 9 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
- US-A-5912212 describes oxidative stable oil lubricating formulations consisting of a hydrocracked paraffinic mineral base oil and 0.1 to 5 wt% of a sulphur or phosphorus containing compound.
- a formulation consisting of a base oil and 3-methyl-5-tert-butyl-4-hydroxy propionic acid ester, dioctylamino-methyltolyltriazole and 0.4 wt% of dilaurylthio-dipropionate.
- the oil had a high oxidative stability.
- US3338877 describes co-polymers of ethylene and stilbene useful as lubricating oils with excellent oxidative and thermal stability. A number of anti-scuffing agents are taught as suitable for addition thereto.
- a mineral-derived base oil has the meaning within the context of this specification that the base oil was obtained from a mineral oil source.
- Polysulfide compounds are represented by the formula (I) R 1 -(S) a -R 2 (I) wherein:
- the copper passivator or electrostatic discharge depressant is the optionally substituted benzotriazole compound represented by the formula (III) wherein R 4 may be hydrogen or a group represented by the formula (IV) or by the formula (V) wherein:
- Preferred compounds are 1-[bis(2-ethylhexyl)-aminomethyl]benzotriazole, methylbenzotriazole, dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole and mixtures thereof.
- Other preferred compounds include (N-Bis(2-ethylhexyl)-aminomethyl-tolutriazole, non-substituted benzotriazole, and 5-methyl-1H-benzotriazole. Examples of copper passivator additives as described above are described in US-A-5912212 , EP-A-1054052 and in US-A-2002/0109127 .
- Copper passivator additives as those described above are commercially available under the product names BTA, TTA, IRGAMET 39, IRGAMET30 and IRGAMET 38S from CIBA Ltd Basel Switzerland, also traded under the trade name Reomet by CIBA.
- the content of the above copper passivator in the oil formulation is between 5 and 1000 mg/kg.
- a practical upper limit may vary depending on the specific application of the oil formulation. For example, when desiring improved dielectric discharge tendencies of the oil for use as electrical oil it may be desired to add a high concentration of the copper passivator additive. Applicants found that the advantages of the invention can be achieved at concentrations below 1000 mg/kg and more preferably below 300 mg/kg, even more preferably below 50mg/kg.
- the oil formulation preferably also comprises an anti-oxidant additive. It has been found that, especially in case the base oil is a mineral paraffinic base oil, the sludge formed and total acidity both measured after the IEC 61125 C oxidation test, which properties are indicators for good oxidation stable oils, are considerably reduced when also an anti-oxidant is present.
- the anti-oxidant may be a so-called hindered phenolic or amine antioxidant, for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenyl-amines or ionol derived hindered phenols.
- hindered phenolic or amine antioxidant for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenyl-amines or ionol derived hindered phenols.
- Sterically hindered phenolic antioxidants of particular interest are selected from the group consisting of 2,6-di-tert-butylphenol (IRGANOX TM L 140, CIBA), di tert-butylated hydroxotoluene (BHT), methylene-4,4'-bis-(2.6-tert-butylphenol), 2,2'-methylene bis-(4,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-hydroxyhydrocinnamate) (IRGANOX TM L109, CIBA), ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)thio) acetic acid, C 10 -C 14 isoalkyl esters (IRGANOX TM L118, CIBA), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C 7 -C 9 alkyl
- amine antioxidants are aromatic amine anti-oxidants for example N,N'-Di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylene-diamine, N,N'-bis(1-methyl-heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylene-diamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphthyl-2-)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbuty
- p,p'-di-tert-octyldiphenylamine 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethyl-aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di(phenylamino)ethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,3-di-(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3
- the content of the anti oxidant additive is preferably less than 2 wt% and more preferably less than 1 wt%.
- the content is preferably less than 0,6 wt% in certain applications, such as when the oil formulation is used as an electrical oil.
- the content of antioxidant is preferably greater than 10 mg/kg.
- the oil formulation preferably has a sulphur content of below 0,5 wt% and even more preferably below 0,15 wt%.
- the source of the majority of the sulphur in the oil formulation will be the sulphur as contained in the base oil component of the oil formulation according the invention.
- the base oil composition preferably has a kinematic viscosity at 100 °C of less than 50 mm 2 /sec, more preferably between 2 and 25 mm 2 /sec, most preferably between 2 and 15 mm 2 /sec.
- the base oil composition preferably has a kinematic viscosity at 40 °C of between 1 and 200 mm 2 /sec, more preferably between 3.5 and 100 mm 2 /sec, most preferably between 5 and 12 mm 2 /sec.
- the viscosity of the base oil composition will also depend on the particular use of the oil formulation. If the oil formulation is used as an electrical oil its kinematic viscosity at 40 °Cis preferably between 1 and 50 mm 2 /sec.
- this electrical oil formulation is a transformer oil
- the base oil will preferably have a kinematic viscosity at 40 °C of between 5 and 15 mm 2 /sec. If the electrical oil is a low temperature switch gear oil the base oil viscosity at 40°C is preferably between 1 and 15 and more preferably between 1 and 4 mm 2 /sec.
- the flash point of the base oil composition as measured by ASTM D92 may be greater than 90 °C, preferably greater than 120 °C, yet more preferably greater than 140 °C, and even more preferably greater than 170 °C.
- the higher flash points are desirable for applications where peak temperatures can exceed the average oil temperature, for instance in applications under high temperature and/or with restricted heat transmission potential. Examples are electric transformers and electric engines.
- the base oil composition may comprise one or more base oils selected from mineral-derived naphthenic base oils and/or mineral-derived paraffic base oils.
- the base oil composition may this comprise a mineral-derived base oil of the so-called paraffinic type or naphthenic type.
- Such base oils are obtained by refinery processes starting from paraffinic and naphthenic crude feeds.
- Mineral-derived naphthenic base oils for the purpose of this invention are defined as having a pour point of below -20 °C and a viscosity index of below 70.
- Mineral-derived paraffin base oils are defined by a viscosity index of greater than 70, preferably greater than 90.
- Mineral-derived naphthenic and paraffin base oils are well known and described in more detail in " Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 28-35 .
- the base oil composition preferably comprises a base oil comprising a series of iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms and wherein n is a number between 20 and 35.
- the paraffin content in the base oil composition is greater than 80 wt%, more preferably greater than 90 wt%, yet more preferably greater than 95%, and again more preferably greater than 98%.
- the base oil composition furthermore may preferably have a content of naphthenic compounds of between 1 and 20 wt%. It has been found that these base oils have a good additive response to the additives listed above when aiming to improve oxidation stability.
- the content of naphthenic compounds and the presence of such a continuous series of iso-paraffins may be measured by Field desorption/Field Ionisation (FD/FI) technique. In this technique the oil sample is first separated into a polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPLC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states.
- HPLC high performance liquid chromatography
- the saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI (a "soft” ionisation technique) is used for the determination of hydrocarbon types in terms of carbon number and hydrogen deficiency.
- FI Field desorption/Field Ionisation
- the type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: C n H 2n+z . Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different iso-paraffins having the same stoichiometry or n-number.
- the results of the mass spectrometer are processed using commercial software (poly 32; available from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type.
- the base oil composition having the continuous isoparaffinic series as described above are preferably obtained by hydroisomerisation of a paraffinic wax, yet more preferably followed by some type of dewaxing, such as solvent or catalytic dewaxing.
- the above described base oil composition may preferably be obtained by hydroisomerisation of a paraffinic wax, preferably followed by a dewaxing treatment, such as a solvent or catalytic dewaxing treatment.
- the paraffinic wax may be a highly paraffinic slack wax.
- the oil formulation may comprise a single type of base oil or blends of the above-described base oils as base oil composition.
- the base oil composition comprises at least 80% by weight of the total formulation of a mineral-derived naphthenic base oil; and to formulations wherein the base oil comprises at least 80% by weight of a mineral-derived paraffinic base oil.
- base oils and other synthetic base oil components may be present in the oil formulation, such as for example esters, poly alpha olefins, as preferably obtained by oligomerisation of an olefinic compound, poly alkylene glycols and the like.
- additives next to the ones described above may also be present in the formulation.
- the type of additives will depend on the specific application. Without intending to be limiting, examples of possible additives are dispersants, detergents, viscosity modifying polymers, hydrocarbon or oxygenated hydrocarbon type pour point depressants, emulsifiers, demulsifiers, antistaining additives and friction modifiers. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526 .
- the dispersant is an ashless dispersant, for example polybutylene succinimide polyamines or Mannic base type dispersants.
- the detergent is an over-based metallic detergent, for example the phosphonate, sulfonate, phenolate or salicylate types as described in the above referred to General Textbook.
- the viscosity modifier is a viscosity modifying polymer, for example polyisobutylenes, olefin copolymers, polymethacrylates and polyalkylstyrenes and hydrogenated polyisoprene star polymer (Shellvis).
- suitable antifoaming agents are polydimethylsiloxanes and polyethylene glycol ethers and esters.
- the oil formulation may find use as turbine oil, gasoline engine oil, diesel engine oil, automotive and industrial gear oils, for example automatic and manual transmission and differential oils, hydraulic machine oil, refrigerator oil, plastic processing oil for rolling, press, forging, sqeezing, draw, punch and the like operations, thermal treating oil, discharge processing oil, slide guide oil, rust proofing oil and heat medium.
- a preferred use of the oil formulation is as electrical oil. Examples of applications are switch gears, transformers, regulators, circuit breakers, power plant reactors, cables and other electrical equipment.
- a problem often encountered when using an electrical oil based on a naphthenic base oil is that the kinematic viscosity at -30 °C is too high.
- Another preferred mixture of aromatic compounds is comprised in a mixture of 2,6-di-t-butyl phenol and 2,6-di-t-butyl cresol.
- the oil formulation comprises between 0.1 and 3 wt% of 2,6-di-t-butyl phenol and 0.1 to 2 wt% of 2,6-di-t-butyl cresol in a weight ratio of between 1:1 and 1:1.5.
- the oil formulation preferably comprising the anti-wear additive, is preferably subjected to an additional clay treatment.
- Clay treatment is a well know treatment to remove polar compounds from the oil formulation. It is performed in order to further improve the color, chemical and thermal stability of the oil formulation. It may be performed prior to adding the additives mentioned in this description on a, partly, formulated oil formulation. Clay treatment processes are for example described in Lubricant base oil and wax processing, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 229-232 .
- the copper passivator and optional anti-oxidant are added after the clay treatment.
- the electrical oil as described above may find use in applications which have to start up regularly, especially more than 10 times per year at a temperature of below 0 °C, more preferably below -5 °C, wherein the temperature of the oil when the application is running is above 0 °C.
- Examples of such applications are as low temperature switch gear oils, transformers, regulators, circuit breakers, power plant reactors, switch gear, cables, electrical equipment.
- Such applications are well known to the skilled person and described for example in Lubricants and related products, Dieter Klamann, Verlag Chemie GmbH, Weinhem, 1984, pages 330-339 .
- the invention will be illustrated with the following non-limiting examples.
- One Fischer-Tropsch derived base oil referred to as GTL BO
- two naphthenic type of base oils referred to as naphthenic-1 and naphthenic-2
- a mineral paraffinic base oil referred to as mineral paraffinic base oil. The properties of these base oils are listed in Table 1.
- Example 1 two formulations A and B were prepared of which the base oil component consisted of 95 wt% of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil. To these mixtures 10 mg/kg of 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole (Reomet38S) was added. To mixture A 200 mg/kg of Dibenzyldisulfide was added and to mixture B 200 mg/kg of Di-n-dodecyldisulfid was added. Oil mixtures A and B were tested with the IEC 61125 C Oxidation test 164h/120 °C test to measure the acidity of the oil phase.
- the base oil component consisted of 95 wt% of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil.
- Reomet38S 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole
- the acidity of the oil phase of mixture A was 0.26 mg KOH/g and the acidity of the oil phase of mixture B was 0.94 mg KOH/g. Both values are very low and illustrate an excellent oxidative stability.
- the values for Mixture A show that even more excellent results are obtained when the preferred Dibenzyldisulfide additive is used as the an organic polysulphide anti-wear additive. It is surprising that the choice of a particular anti-wear additive can improve the oxidation stability in the manner here illustrated.
- Table 3 Total Acidity formation according to IEC 61125 C Additivation scheme 1 2 3 4 5 Dibenzyldisulfide mg/kg - - 200 200 200 1-[bis(2-ethylhexyl)aminomethyl]-benzotriazole mg/kg - 10 - 10 10
- Antioxidant BHT Wt% - - - - 0,08 Total acidity according to IEC 61125 C Naphthenic base oil-1 Mg KOH/g 4,14 3,87 1,59 0,83 1,02 Paraffinic base oil-1 Mg KOH/g 9,12 6,78 0,78 0,38 0,02 GTL Base Oil-1 Mg KOH/g 13,67 10,55 12,65 12,57 0,10
- oil mixtures were prepared according to the scheme as presented in Table 4. Two oil mixtures were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Muenchen (D). The anti-oxidant and copper passivator additives were added after the clay treatment. The properties of the oil mixtures were measured and the oil mixtures were subjected to the IEC OXIDATION TEST at 500h/120 °C.
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Description
- The invention is related to an oxidation stable oil formulation comprising a base oil composition and additives.
-
US-A-6790386 describes a dielectric fluid comprising an iso-paraffin base oil and additives. The iso-paraffin base oil is prepared by hydrotreating, hydroisomerisation and hydrogenation of a paraffinic vacuum feedstock. -
US-A-6214776 describes a formulation comprising a paraffinic base oil and an additive package containing a hindered phenol antioxidant and a metal deactivator, for use as load tap changer or transformer oil. According to this publication, base oils having a kinematic viscosity at 40 °C of between 5 and 20 cSt can be used as base oil in formulations such as electrical oils or transformer oils. -
US-A-5241003 discloses a combination of a sulfur-containing antiwear additive and a carboxylic derivative dispersant for use as additive package for lubricants. -
US-A-5773391 describes a composition comprising a polyol ester base oil, an aliphatic monocarboxylic acid mixture, and an additive package comprising an antioxidant and a metal deactivator. The document further discloses phosphorodithionates as antiwear additives. -
WO-A-02070629 -
US-A-5912212 describes oxidative stable oil lubricating formulations consisting of a hydrocracked paraffinic mineral base oil and 0.1 to 5 wt% of a sulphur or phosphorus containing compound. In the examples a formulation consisting of a base oil and 3-methyl-5-tert-butyl-4-hydroxy propionic acid ester, dioctylamino-methyltolyltriazole and 0.4 wt% of dilaurylthio-dipropionate. The oil had a high oxidative stability. -
US3338877 describes co-polymers of ethylene and stilbene useful as lubricating oils with excellent oxidative and thermal stability. A number of anti-scuffing agents are taught as suitable for addition thereto. - A demand is acknowledged for high oxidation resistant oil products for use as for example electrical oil, in particular as a transformer oil or a switch gear oil, preferably without high additive treat rates due to adverse effects on other properties than oxidation stability.
- This aim is achieved with the oil formulation defined in claim 1.
- Applicants found that an oil formulation is achieved having a very high oxidation stability, however not requiring a high treat rate.
- Applicants found that when a mineral-derived base oil of the so-called paraffinic type and/or naphthenic type, base oil is combined with at least one copper passivator selected from optionally substituted benzotriazole compounds represented by the formula (III) and a low content of an anti-wear additive comprising an organic polysulfide represented by the formula (I), an oil product is obtained which has properties highly suitable for use as an electrical oil. It was not to be expected that the combination of the copper passivator and a small amount of an anti-wear additive would result in such an improvement in oxidative stability. A mineral-derived base oil has the meaning within the context of this specification that the base oil was obtained from a mineral oil source.
- Polysulfide compounds are represented by the formula (I)
R1-(S)a-R2 (I)
wherein: - a is 2, 3, 4 or 5, preferably 2;
- R1 and R2 may be the same or different and each may be straight or branched alkyl group of 1 to 22 carbon atoms, aryl groups of 6-20 carbon atoms, alkylaryl groups of 7-20 carbon atoms or arylalkyl groups of 7-20 carbon atoms. Preferred are arylalkyl groups, more preferred are optionally substituted benzyl groups. More preferably R1 and R2 are independently selected from a benzyl group or a straight or branched dodecyl group. Examples of possible sulphur and phosphorus containing compounds and the preferred compounds mentioned here are described in the aforementioned
US-A-5912212 as its component (b). Examples of suitable disulfide compounds are dibenzyldisulfide,ditertdodecyldisulfide and didodecyldisulfide. The content of the anti-wear additive in the oil formulation is preferably less than formulation 800 mg/kg and even more preferably less than 400 mg/kg. The lower limit is 10 mg/kg, most preferably 50 mg/kg. -
- c is 0, 1, 2 or 3;
- R3 is a straight or branched C1-4 alkyl group. Preferably R3 is methyl or ethyl and C is 1 or 2. R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms, preferably of 4-9 carbon atoms.
- Preferred compounds are 1-[bis(2-ethylhexyl)-aminomethyl]benzotriazole, methylbenzotriazole, dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole and mixtures thereof. Other preferred compounds include (N-Bis(2-ethylhexyl)-aminomethyl-tolutriazole, non-substituted benzotriazole, and 5-methyl-1H-benzotriazole. Examples of copper passivator additives as described above are described in
US-A-5912212 ,EP-A-1054052 and inUS-A-2002/0109127 . These benzotriazoles compounds are preferred because they also act as an electrostatic discharge depressant, which is beneficial when the oil formulation is used as an electrical oil. Copper passivator additives as those described above are commercially available under the product names BTA, TTA, IRGAMET 39, IRGAMET30 and IRGAMET 38S from CIBA Ltd Basel Switzerland, also traded under the trade name Reomet by CIBA. - The content of the above copper passivator in the oil formulation is between 5 and 1000 mg/kg. A practical upper limit may vary depending on the specific application of the oil formulation. For example, when desiring improved dielectric discharge tendencies of the oil for use as electrical oil it may be desired to add a high concentration of the copper passivator additive. Applicants found that the advantages of the invention can be achieved at concentrations below 1000 mg/kg and more preferably below 300 mg/kg, even more preferably below 50mg/kg.
- The oil formulation preferably also comprises an anti-oxidant additive. It has been found that, especially in case the base oil is a mineral paraffinic base oil, the sludge formed and total acidity both measured after the IEC 61125 C oxidation test, which properties are indicators for good oxidation stable oils, are considerably reduced when also an anti-oxidant is present. The anti-oxidant may be a so-called hindered phenolic or amine antioxidant, for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenyl-amines or ionol derived hindered phenols. Sterically hindered phenolic antioxidants of particular interest are selected from the group consisting of 2,6-di-tert-butylphenol (IRGANOX TM L 140, CIBA), di tert-butylated hydroxotoluene (BHT), methylene-4,4'-bis-(2.6-tert-butylphenol), 2,2'-methylene bis-(4,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-hydroxyhydrocinnamate) (IRGANOX TM L109, CIBA), ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)thio) acetic acid, C10-C14isoalkyl esters (IRGANOX TM L118, CIBA), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9alkyl esters (IRGANOX TM L135, CIBA,) tetrakis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl)methane (IRGANOX TM 1010, CIBA), thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1035, CIBA), octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1076, CIBA) and 2,5-di-tert-butylhydroquinone. These products are known and are commercially available. Of most particular interest is 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid-C7-C9-alkyl ester.
- Examples of amine antioxidants are aromatic amine anti-oxidants for example N,N'-Di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylene-diamine, N,N'-bis(1-methyl-heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylene-diamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphthyl-2-)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N'-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluene-sulfoamido)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethyl-aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di(phenylamino)ethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,3-di-(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, tert-octylated phenothiazine, 3,7-di-tert-octylphenothiazine. Also possible amine antioxidants are those according to formula VIII and IX of
EP-A-1054052 , which compounds are also described inUS-A-4,824,601 . - The content of the anti oxidant additive is preferably less than 2 wt% and more preferably less than 1 wt%. The content is preferably less than 0,6 wt% in certain applications, such as when the oil formulation is used as an electrical oil. The content of antioxidant is preferably greater than 10 mg/kg.
- The oil formulation preferably has a sulphur content of below 0,5 wt% and even more preferably below 0,15 wt%. The source of the majority of the sulphur in the oil formulation will be the sulphur as contained in the base oil component of the oil formulation according the invention.
- The base oil composition preferably has a kinematic viscosity at 100 °C of less than 50 mm2/sec, more preferably between 2 and 25 mm2/sec, most preferably between 2 and 15 mm2/sec. The base oil composition preferably has a kinematic viscosity at 40 °C of between 1 and 200 mm2/sec, more preferably between 3.5 and 100 mm2/sec, most preferably between 5 and 12 mm2/sec. The viscosity of the base oil composition will also depend on the particular use of the oil formulation. If the oil formulation is used as an electrical oil its kinematic viscosity at 40 °Cis preferably between 1 and 50 mm2/sec. More preferably, if this electrical oil formulation is a transformer oil, the base oil will preferably have a kinematic viscosity at 40 °C of between 5 and 15 mm2/sec. If the electrical oil is a low temperature switch gear oil the base oil viscosity at 40°C is preferably between 1 and 15 and more preferably between 1 and 4 mm2/sec.
- The flash point of the base oil composition as measured by ASTM D92 may be greater than 90 °C, preferably greater than 120 °C, yet more preferably greater than 140 °C, and even more preferably greater than 170 °C. The higher flash points are desirable for applications where peak temperatures can exceed the average oil temperature, for instance in applications under high temperature and/or with restricted heat transmission potential. Examples are electric transformers and electric engines.
- The base oil composition may comprise one or more base oils selected from mineral-derived naphthenic base oils and/or mineral-derived paraffic base oils.
- The base oil composition may this comprise a mineral-derived base oil of the so-called paraffinic type or naphthenic type. Such base oils are obtained by refinery processes starting from paraffinic and naphthenic crude feeds. Mineral-derived naphthenic base oils for the purpose of this invention are defined as having a pour point of below -20 °C and a viscosity index of below 70. Mineral-derived paraffin base oils are defined by a viscosity index of greater than 70, preferably greater than 90. Mineral-derived naphthenic and paraffin base oils are well known and described in more detail in "Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 28-35.
- Applicants found that very good oxidative stable oil formulations can be obtained when the base oil composition has a saturates content as measured by IP386 of preferably greater than 98 wt%, more preferably greater than 99 wt% and even more preferably greater than 99.5 wt% as measured on fresh base oil.
- The base oil composition preferably comprises a base oil comprising a series of iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms and wherein n is a number between 20 and 35.
- Preferably, the paraffin content in the base oil composition is greater than 80 wt%, more preferably greater than 90 wt%, yet more preferably greater than 95%, and again more preferably greater than 98%.
- The base oil composition furthermore may preferably have a content of naphthenic compounds of between 1 and 20 wt%. It has been found that these base oils have a good additive response to the additives listed above when aiming to improve oxidation stability. The content of naphthenic compounds and the presence of such a continuous series of iso-paraffins may be measured by Field desorption/Field Ionisation (FD/FI) technique. In this technique the oil sample is first separated into a polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPLC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states. The saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI (a "soft" ionisation technique) is used for the determination of hydrocarbon types in terms of carbon number and hydrogen deficiency. The type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: CnH2n+z. Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different iso-paraffins having the same stoichiometry or n-number. The results of the mass spectrometer are processed using commercial software (poly 32; available from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type.
- The base oil composition having the continuous isoparaffinic series as described above are preferably obtained by hydroisomerisation of a paraffinic wax, yet more preferably followed by some type of dewaxing, such as solvent or catalytic dewaxing.
- The above described base oil composition may preferably be obtained by hydroisomerisation of a paraffinic wax, preferably followed by a dewaxing treatment, such as a solvent or catalytic dewaxing treatment. The paraffinic wax may be a highly paraffinic slack wax.
- The oil formulation may comprise a single type of base oil or blends of the above-described base oils as base oil composition. The base oil composition comprises at least 80% by weight of the total formulation of a mineral-derived naphthenic base oil; and to formulations wherein the base oil comprises at least 80% by weight of a mineral-derived paraffinic base oil.
- Also further base oils and other synthetic base oil components may be present in the oil formulation, such as for example esters, poly alpha olefins, as preferably obtained by oligomerisation of an olefinic compound, poly alkylene glycols and the like.
- Additional additives next to the ones described above may also be present in the formulation. The type of additives will depend on the specific application. Without intending to be limiting, examples of possible additives are dispersants, detergents, viscosity modifying polymers, hydrocarbon or oxygenated hydrocarbon type pour point depressants, emulsifiers, demulsifiers, antistaining additives and friction modifiers. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526. Suitably the dispersant is an ashless dispersant, for example polybutylene succinimide polyamines or Mannic base type dispersants. Suitably the detergent is an over-based metallic detergent, for example the phosphonate, sulfonate, phenolate or salicylate types as described in the above referred to General Textbook. Suitably the viscosity modifier is a viscosity modifying polymer, for example polyisobutylenes, olefin copolymers, polymethacrylates and polyalkylstyrenes and hydrogenated polyisoprene star polymer (Shellvis). Examples of suitable antifoaming agents are polydimethylsiloxanes and polyethylene glycol ethers and esters.
- The oil formulation may find use as turbine oil, gasoline engine oil, diesel engine oil, automotive and industrial gear oils, for example automatic and manual transmission and differential oils, hydraulic machine oil, refrigerator oil, plastic processing oil for rolling, press, forging, sqeezing, draw, punch and the like operations, thermal treating oil, discharge processing oil, slide guide oil, rust proofing oil and heat medium. A preferred use of the oil formulation is as electrical oil. Examples of applications are switch gears, transformers, regulators, circuit breakers, power plant reactors, cables and other
electrical equipment. A problem often encountered when using an electrical oil based on a naphthenic base oil is that the kinematic viscosity at -30 °C is too high. When such an oil would be used in application which have to start up at low temperatures, especially at temperatures below 0 °C, the higher viscosity will have a negative effect on the required heat dissipation of the electrical oil. Overheating of the equipment can result. In order to improve the gassing tendency of the oil formulation it is preferred to add between 0.05 and 10 wt%, preferably between 0.1 and 5 wt% of an aromatic compound. Preferred aromatic compounds are for example tertrahydronaphthalene, diethylbenzene, diisopropylbenzene, a mixture of alkylbenzenes as commercially obtainable as "Shell Oil 4697" or "Shellsol A 150" both "Shell" products obtainable from Shell Deutschland GmbH. Another preferred mixture of aromatic compounds is comprised in a mixture of 2,6-di-t-butyl phenol and 2,6-di-t-butyl cresol. Preferably the oil formulation comprises between 0.1 and 3 wt% of 2,6-di-t-butyl phenol and 0.1 to 2 wt% of 2,6-di-t-butyl cresol in a weight ratio of between 1:1 and 1:1.5. - The oil formulation, preferably comprising the anti-wear additive, is preferably subjected to an additional clay treatment. Clay treatment is a well know treatment to remove polar compounds from the oil formulation. It is performed in order to further improve the color, chemical and thermal stability of the oil formulation. It may be performed prior to adding the additives mentioned in this description on a, partly, formulated oil formulation. Clay treatment processes are for example described in Lubricant base oil and wax processing, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 229-232. Preferably the copper passivator and optional anti-oxidant are added after the clay treatment.
- The electrical oil as described above may find use in applications which have to start up regularly, especially more than 10 times per year at a temperature of below 0 °C, more preferably below -5 °C, wherein the temperature of the oil when the application is running is above 0 °C. Examples of such applications are as low temperature switch gear oils, transformers, regulators, circuit breakers, power plant reactors, switch gear, cables, electrical equipment. Such applications are well known to the skilled person and described for example in Lubricants and related products, Dieter Klamann, Verlag Chemie GmbH, Weinhem, 1984, pages 330-339.
- The invention will be illustrated with the following non-limiting examples. In the examples use has been made of four different types of base oils. One Fischer-Tropsch derived base oil, referred to as GTL BO, two naphthenic type of base oils, referred to as naphthenic-1 and naphthenic-2, and a mineral paraffinic base oil. The properties of these base oils are listed in Table 1.
Table 1 Base Oil GTL BO -1 GTL BO-2 GTL BO-3 Naphthenic-1 Naphthenic-2 Paraffinic -1 Paraffinic -2 Vk @ 100°C ASTM D445 mm2/s 2,4 4.0 7.8 2,1 2,1 2,2 8,3 Vk @ 40°C ASTM D445 mm2/s 7,9 8,8 7,8 8,0 75,1 VI ASTM D2270 126 135 148 <0 47 88 73 Pour Point ASTM D5950 °C -51 -30 -24 -60 -60 -15 -18 Flash point ASTM D92 °C 192 228 274 147 154 186 232 Paraffins by FD/FI technique (wt%) 90.7 92.3 90.8 Carbon distribution See Figure 1(*) Figure 2(*) Basic Nitrogen ISO 3771mod mg/kg 4 <1 1 3 Sulphur ISO 14596 %m <0,001 0,075 0,001 0,015 0,021 Colour ASTM D2049 L0.5 L0.5 L0.5 L0.5 L1.5 Biodegradation after 28 days ISO 14593 % 60 (*) Carbon distribution per carbon number as measured by Field desorption/Field Ionisation (FD/FI) technique, wherein Z=2 represents the iso and normal paraffins, Z=0 the 1-ring naphthenic compounds, Z=-2 the 2-ring naphthenic compounds, Z=-4 the 3-ring naphthenic compounds etc. - In Example 1 two formulations A and B were prepared of which the base oil component consisted of 95 wt% of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil. To these mixtures 10 mg/kg of 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole (Reomet38S) was added. To mixture A 200 mg/kg of Dibenzyldisulfide was added and to mixture B 200 mg/kg of Di-n-dodecyldisulfid was added. Oil mixtures A and B were tested with the IEC 61125 C Oxidation test 164h/120 °C test to measure the acidity of the oil phase. The acidity of the oil phase of mixture A was 0.26 mg KOH/g and the acidity of the oil phase of mixture B was 0.94 mg KOH/g. Both values are very low and illustrate an excellent oxidative stability. The values for Mixture A show that even more excellent results are obtained when the preferred Dibenzyldisulfide additive is used as the an organic polysulphide anti-wear additive. It is surprising that the choice of a particular anti-wear additive can improve the oxidation stability in the manner here illustrated.
- Starting with the mineral-derived naphthenic-1, mineral-derived paraffin base oil and the GTL base oil-1 of Table 1 five different oil mixtures according to the additivation schemes 1-5 of table 2 were made. For all of these oil mixtures the Sludge Formation was measured according to the Oxidation Test IEC 61125 C at 164h/120°C. The lower the value the less sludge is found. The results are also presented in Table 2.
- From Table 2 it can be seen that the combination of the organic polysulphide anti-wear additive and the copper passivator result in a remarkable low sludge Formation for mineral naphthenic and mineral paraffinic base oils. Especially for the mineral paraffin base oils the presence of an anti-oxidant further reduces the sludge formation significantly.
Table 2 Sludge formation according to IEC 61125 C Additivation scheme 1 2 3 4 5 Dibenzyldisulfide mg/kg - - 200 200 200 1-[bis(2-ethylhexyl)-aminomethyl]benzotriazole (Reomet38S) mg/kg - 10 - 10 10 Antioxidant BHT %m - - - - 0,08 Naphthenic base oil Sludge 1,700 1,530 0,561 0,281 0,295 Paraffinic base oil-1 Sludge 3,340 2,440 0,209 0,086 <0,006 GtL base oil-1 Sludge 0,085 0,023 0,043 0,071 0,006 - For all of these oil mixtures according to additivation schemes 1-5 of above also the Total Acidity using the Oxidation Test IEC 61125 C at 164h/120 °C was measured. The lower the value the less acid compounds are formed and the more oxidative stable the oil formulation is. The results are presented in Table 3.
Table 3 Total Acidity formation according to IEC 61125 C Additivation scheme 1 2 3 4 5 Dibenzyldisulfide mg/kg - - 200 200 200 1-[bis(2-ethylhexyl)aminomethyl]-benzotriazole mg/kg - 10 - 10 10 Antioxidant BHT Wt% - - - - 0,08 Total acidity according to IEC 61125 C Naphthenic base oil-1 Mg KOH/g 4,14 3,87 1,59 0,83 1,02 Paraffinic base oil-1 Mg KOH/g 9,12 6,78 0,78 0,38 0,02 GTL Base Oil-1 Mg KOH/g 13,67 10,55 12,65 12,57 0,10 - 4 oil mixtures were prepared according to the scheme as presented in Table 4. Two oil mixtures were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Muenchen (D). The anti-oxidant and copper passivator additives were added after the clay treatment. The properties of the oil mixtures were measured and the oil mixtures were subjected to the IEC OXIDATION TEST at 500h/120 °C.
Table 4 Sample Identification U V X Y Z W GTL base oil-1 Wt% 99,61 99,3 99,68 - 94,68 - Naphthenic-1 Wt% - 99,68 94,68 Mineral paraffinic base oil-1 Wt% - - 5,00 5,00 Dibenzyldisulfid Wt% 0,09 0,4 0,02 0,02 0,02 0,02 Clay treatment (Tonsil) % - - 1 1 1-[bis(2-ethylhexyl)aminomethyl]-benzotriazole mg/kg 10 10 10 10 10 10 Antioxidant BHT Wt% 0,30 0,30 0,30 0,30 0,30 0,30 Properties of the oil mixtures U V X Y Z W FLASH POINT ISO 2719 160 145 160 145 POUR POINT °C DIN ISO 3016 <-60 <-60 -51 -54 KIN.VISCOSITY -30 °C mm2/s DIN 51562 341 1140 368 1210 KIN.VISCOSITY 40 °C mm2/s DIN 51562 8 8,7 8 9 KIN.VISCOSITY 100 °C mm2/s DIN 51562 2,4 2,2 2,4 2,2 BREAKDOWN VOLTAGE kV VDE 0370-5 84 DIELECTR. DISSIPATION FACTOR 90°C VDE VDE 0370-1 0,0002 KORRO. SULFUR Ag/100°C DIN 53 353 Fail (*) Fail (**) pass pass IEC OXIDATION TEST 500h/120°C: IEC 61125/C - Total acidity after 500h/120°C test mgKOH/ g IEC 61125/C <0,01 0,69 0,02 0,41 - Sludge after 500h/120°C test m % IEC 61125/C <0,006 0,202 <0,006 0,043 - Dielectr. Dissip. F. 90°C after 500h/120°C test IEC 61125/C 0,0015 0,102 1 <0,003 5 0,1017 (*) light grey discolouration
(**) grey discolouration
Claims (13)
- Oxidation stable oil formulation comprising a base oil composition, said base oil composition comprising at least 80% by weight of a mineral-derived naphthenic base oil or at least 80% by weight of a mineral-derived paraffinic base oil, a content of between 5 and 1000 mg/kg of a copper passivator selected from optionally substituted benzotriazole compounds represented by the formula (III)c is 0, 1, 2 or 3;R3 is a straight or branched C1-4 alkyl group; R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms; from 0.001 wt% to less than 0.1 wt% of an anti-wear additive is selected from organic polysulfides represented by the formula
R1-(S)a-R2 (I)
wherein:a is 2, 3, 4 or 5;R1 and R2 are independently selected from the group consisting of optionally substituted, straight or branched, saturated or unsaturated C1-C25 hydrocarbon groups. - Formulation according to claim 1, wherein R1 and R2 are independently selected from the group consisting of optionally substituted, straight or branched, aromatic or aliphatic C4-C20, preferably C6-C14 hydrocarbon groups.
- Formulation according to claim 1 or 2, wherein R1 and R2 are independently selected from straight or branched dodecyl and benzyl.
- Formulation according to one or more of the preceding claims, wherein the content of anti-wear additive in the formulation is less than 800 mg/kg, more preferably less than 400 mg/kg.
- Formulation according to any preceding claim, wherein R3 is methyl or ethyl and C is 1 or 2.
- Formulation according to any one of claims 1-5, wherein the formulation has a sulphur content of below 0.5 wt%.
- Formulation according to any one of claims 1-6 wherein the formulation also contains greater than 10 mg/kg to less than 0.6 wt% of an antioxidant additive wherein the antioxidant additive is a phenolic or amine antioxidant.
- Formulation according to claim 7, wherein the anti-oxidant additive is ditert.-butylated hydroxotoluene.
- Formulation according to any one of claims 1-8, wherein the kinematic viscosity at 40 °C of the base oil composition is between 1 and 4 mm2/sec.
- Formulation according to any one of claims 1-8, wherein the kinematic viscosity at 40 °C of the base oil composition is between 5 and 15 mm2/sec.
- Process to prepare a formulation according to any one of claims 1-6, wherein a mixture of the base oil composition and the organic sulphur anti-wear additive is subjected to a clay treatment and wherein the copper passivator is added after performing the clay treatment.
- Use of the formulation according to one or more of the preceding claims as an electrical oil.
- Use of the formulation according to claim 12 as a transformer oil.
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EP06777414.1A EP1896556B1 (en) | 2005-06-23 | 2006-06-22 | Oxidative stable oil formulation |
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EP06777414.1A EP1896556B1 (en) | 2005-06-23 | 2006-06-22 | Oxidative stable oil formulation |
PCT/EP2006/063433 WO2006136591A1 (en) | 2005-06-23 | 2006-06-22 | Oxidative stable oil formulation |
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EP (1) | EP1896556B1 (en) |
JP (1) | JP5420241B2 (en) |
KR (1) | KR20080025746A (en) |
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Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5282087B2 (en) * | 2007-06-13 | 2013-09-04 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Integrated hydroprocessing with high productivity catalysts |
US20090001330A1 (en) * | 2007-06-28 | 2009-01-01 | Chevron U.S.A. Inc. | Electrical Insulating Oil Compositions and Preparation Thereof |
US20100279904A1 (en) * | 2007-07-31 | 2010-11-04 | Chevron U.S.A. Inc. | Electrical insulating oil compositions and preparation thereof |
CN101796170B (en) * | 2007-08-13 | 2014-07-02 | 国际壳牌研究有限公司 | Lubricating base oil blend |
JP5165307B2 (en) * | 2007-08-23 | 2013-03-21 | Jx日鉱日石エネルギー株式会社 | Electrical insulating oil and method for producing the same |
BRPI0819886A2 (en) * | 2007-12-07 | 2015-06-16 | Shell Int Research | Base oil formulation, use of a fischer-tropsch-derived light base oil, and methods for improving a property of a base oil formation and for preparing a base oil formulation |
EP2072610A1 (en) * | 2007-12-11 | 2009-06-24 | Shell Internationale Research Maatschappij B.V. | Carrier oil composition |
US20100107479A1 (en) * | 2008-11-04 | 2010-05-06 | Duncan Richardson | Antifoam fuel additives |
US20100107482A1 (en) | 2008-11-06 | 2010-05-06 | Bennett Joshua J | Conductivity-improving additives for fuel |
CN102459533B (en) * | 2009-05-01 | 2015-01-28 | 国际壳牌研究有限公司 | Functional fluid compositions with improved seal swell properties |
DE102009030061A1 (en) * | 2009-06-22 | 2010-12-30 | Chemische Werke Kluthe Gmbh | Synthetic oil, its use and an additive combination |
WO2010149706A1 (en) | 2009-06-24 | 2010-12-29 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
JP5876489B2 (en) * | 2010-09-17 | 2016-03-02 | ダウ グローバル テクノロジーズ エルエルシー | Thermally stable dielectric fluid |
EP2652096A1 (en) * | 2010-12-17 | 2013-10-23 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
WO2012137350A1 (en) * | 2011-04-08 | 2012-10-11 | 三菱電機株式会社 | Process for suppressing copper sulphide production |
JP5731306B2 (en) * | 2011-07-21 | 2015-06-10 | 昭和シェル石油株式会社 | Two-phase lubricating oil composition |
WO2013062890A1 (en) | 2011-10-27 | 2013-05-02 | The Lubrizol Corporation | Lubricants with improved seal compatibility |
JP6266606B2 (en) * | 2012-06-21 | 2018-01-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイShell Internationale Research Maatschappij Besloten Vennootshap | Lubricating oil composition comprising heavy Fischer-Tropsch derived and alkylated aromatic base oil |
JP2016009553A (en) * | 2014-06-23 | 2016-01-18 | 出光興産株式会社 | Electrical insulation oil composition |
CN104130829B (en) * | 2014-07-02 | 2016-08-24 | 安徽吉思特智能装备有限公司 | A kind of transformer oil of antioxidant anticorrosive containing multiple nanoparticle and preparation method thereof |
RU2565763C1 (en) * | 2014-07-31 | 2015-10-20 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Hydraulic oil for industrial equipment |
CN104194885A (en) * | 2014-08-13 | 2014-12-10 | 铜陵日科电子有限责任公司 | Transformer oil containing lanthanum oxide-aluminum nitride nano-particles and preparation method of transformer oil |
CN104212549A (en) * | 2014-08-13 | 2014-12-17 | 铜陵日科电子有限责任公司 | Oxidation corrosion-resistant nanometer aluminum nitride transformer oil containing pine tar, and preparation method thereof |
CN105974097B (en) * | 2016-05-04 | 2017-10-20 | 西安交通大学 | A kind of nano modification transformer oil method for analyzing stability |
RU2642459C1 (en) * | 2017-04-17 | 2018-01-25 | Общество с ограниченной ответственностью "Союзпроминвест" (ООО "Союзпроминвест") | Motor oil for two-valve petrol engines |
RU2653541C1 (en) * | 2017-07-05 | 2018-05-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский государственный энергетический университет" (ФГБОУ ВО "КГЭУ") | Transformer oil oxidation retardation method |
EP3943582B1 (en) * | 2019-03-20 | 2024-05-29 | ENEOS Corporation | Lubricating oil composition |
RU2737521C1 (en) * | 2020-01-21 | 2020-12-01 | Акционерное общество "НПЦ Спецнефтьпродукт" | Method of producing hydraulic oils base (embodiments) |
JP2023520456A (en) * | 2020-03-30 | 2023-05-17 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | thermal management system |
CN114181761A (en) * | 2021-12-10 | 2022-03-15 | 安美科技股份有限公司 | Cleaning-free copper-aluminum sheet punching oil |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1052700A (en) * | 1963-12-09 | 1900-01-01 | ||
GB8332797D0 (en) * | 1983-12-08 | 1984-01-18 | Ciba Geigy Ag | Antioxidant production |
GB8607157D0 (en) * | 1986-03-22 | 1986-04-30 | Ciba Geigy Ag | Lubricating compositions |
US5059299A (en) * | 1987-12-18 | 1991-10-22 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils |
US4943672A (en) * | 1987-12-18 | 1990-07-24 | Exxon Research And Engineering Company | Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403) |
JPH083964B2 (en) * | 1989-08-16 | 1996-01-17 | 三菱電機株式会社 | Oil-filled electrical equipment |
US5241003A (en) * | 1990-05-17 | 1993-08-31 | Ethyl Petroleum Additives, Inc. | Ashless dispersants formed from substituted acylating agents and their production and use |
JP3133201B2 (en) * | 1993-10-29 | 2001-02-05 | 日石三菱株式会社 | Hydraulic oil composition |
BR9504838A (en) * | 1994-11-15 | 1997-10-07 | Lubrizol Corp | Polyol ester lubricating oil composition |
US5912212A (en) * | 1995-12-28 | 1999-06-15 | Nippon Oil Co., Ltd. | Lubricating oil composition |
US6475960B1 (en) * | 1998-09-04 | 2002-11-05 | Exxonmobil Research And Engineering Co. | Premium synthetic lubricants |
JP2000164034A (en) * | 1998-11-30 | 2000-06-16 | Nippon Mitsubishi Oil Corp | Electric insulating oil |
EP1054052B1 (en) * | 1999-05-19 | 2006-06-28 | Ciba SC Holding AG | Stabilized hydrotreated and hydrodewaxed lubricant compositions |
US6214776B1 (en) * | 1999-05-21 | 2001-04-10 | Exxon Research And Engineering Company | High stress electrical oil |
EP1200540A4 (en) * | 1999-05-24 | 2008-09-03 | Lubrizol Corp | Mineral gear oils and transmission fluids |
US6315920B1 (en) * | 1999-09-10 | 2001-11-13 | Exxon Research And Engineering Company | Electrical insulating oil with reduced gassing tendency |
EP1632555B1 (en) * | 2000-02-09 | 2012-12-19 | Citizen Holdings Co., Ltd. | Lubricating oil composition and watch using the same |
US6790386B2 (en) * | 2000-02-25 | 2004-09-14 | Petro-Canada | Dielectric fluid |
JP4789335B2 (en) * | 2001-01-04 | 2011-10-12 | 昭和シェル石油株式会社 | Abrasion resistant lubricating oil composition |
US7132042B2 (en) * | 2002-10-08 | 2006-11-07 | Exxonmobil Research And Engineering Company | Production of fuels and lube oils from fischer-tropsch wax |
US7704379B2 (en) * | 2002-10-08 | 2010-04-27 | Exxonmobil Research And Engineering Company | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate |
-
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