EP2162518A1 - Lubricant compositions stabilized with styrenated phenolic antioxidant - Google Patents
Lubricant compositions stabilized with styrenated phenolic antioxidantInfo
- Publication number
- EP2162518A1 EP2162518A1 EP08771877A EP08771877A EP2162518A1 EP 2162518 A1 EP2162518 A1 EP 2162518A1 EP 08771877 A EP08771877 A EP 08771877A EP 08771877 A EP08771877 A EP 08771877A EP 2162518 A1 EP2162518 A1 EP 2162518A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- antioxidant
- group
- independent
- hydrogen
- oils
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000000314 lubricant Substances 0.000 title claims abstract description 20
- 239000002530 phenolic antioxidant Substances 0.000 title abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 45
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 37
- 239000010687 lubricating oil Substances 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 125000005266 diarylamine group Chemical group 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims description 37
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 235000013824 polyphenols Nutrition 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 125000005504 styryl group Chemical group 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000006078 metal deactivator Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 37
- 235000019198 oils Nutrition 0.000 description 37
- -1 alicyclic radical Chemical class 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- 239000010705 motor oil Substances 0.000 description 17
- 238000009472 formulation Methods 0.000 description 14
- 239000002199 base oil Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 8
- 239000010723 turbine oil Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000010689 synthetic lubricating oil Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000000913 palmityl 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])C([H])([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 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002958 pentadecyl 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])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 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RNBMWJIBIBMXDK-UHFFFAOYSA-N 2,3-dibutyl-N-phenylaniline Chemical compound C(CCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCC RNBMWJIBIBMXDK-UHFFFAOYSA-N 0.000 description 1
- NKDGTVOAKIWRHV-UHFFFAOYSA-N 2-[2-hydroxy-5-methyl-3-(1-phenylethyl)phenyl]sulfanyl-4-methyl-6-(1-phenylethyl)phenol Chemical compound C=1C(C)=CC(SC=2C(=C(C(C)C=3C=CC=CC=3)C=C(C)C=2)O)=C(O)C=1C(C)C1=CC=CC=C1 NKDGTVOAKIWRHV-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- JWXNJZPOYUARDX-UHFFFAOYSA-N 2-tert-butyl-n-phenyl-n-(2,4,4-trimethylpentan-2-yl)aniline Chemical class C=1C=CC=C(C(C)(C)C)C=1N(C(C)(C)CC(C)(C)C)C1=CC=CC=C1 JWXNJZPOYUARDX-UHFFFAOYSA-N 0.000 description 1
- NDACNGSDAFKTGE-UHFFFAOYSA-N 3-hydroxydiphenylamine Chemical compound OC1=CC=CC(NC=2C=CC=CC=2)=C1 NDACNGSDAFKTGE-UHFFFAOYSA-N 0.000 description 1
- FWSYWGNMRGFULE-UHFFFAOYSA-N 4-(2-methylpropyl)-2-(1-phenylethyl)phenol Chemical compound CC(C)CC1=CC=C(O)C(C(C)C=2C=CC=CC=2)=C1 FWSYWGNMRGFULE-UHFFFAOYSA-N 0.000 description 1
- ZNGSTRDJHPHZLZ-UHFFFAOYSA-N 4-ethyl-2,6-bis(1-phenylethyl)phenol Chemical compound OC=1C(C(C)C=2C=CC=CC=2)=CC(CC)=CC=1C(C)C1=CC=CC=C1 ZNGSTRDJHPHZLZ-UHFFFAOYSA-N 0.000 description 1
- IVDRPWARFHGOAE-UHFFFAOYSA-N 4-ethyl-2,6-bis(1-phenylprop-1-en-2-yl)phenol Chemical compound OC=1C(C(C)=CC=2C=CC=CC=2)=CC(CC)=CC=1C(C)=CC1=CC=CC=C1 IVDRPWARFHGOAE-UHFFFAOYSA-N 0.000 description 1
- WXNNCGBQDKCCTQ-UHFFFAOYSA-N 4-ethyl-2-(1-phenylethyl)phenol Chemical compound CCC1=CC=C(O)C(C(C)C=2C=CC=CC=2)=C1 WXNNCGBQDKCCTQ-UHFFFAOYSA-N 0.000 description 1
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 1
- QFCGHEBLSUPGPF-UHFFFAOYSA-N 4-methyl-2,6-bis(1-phenylethyl)phenol Chemical compound C=1C(C)=CC(C(C)C=2C=CC=CC=2)=C(O)C=1C(C)C1=CC=CC=C1 QFCGHEBLSUPGPF-UHFFFAOYSA-N 0.000 description 1
- JYLODCHTTBBBEF-UHFFFAOYSA-N 4-methyl-2,6-bis(1-phenylprop-1-en-2-yl)phenol Chemical compound C=1C(C)=CC(C(C)=CC=2C=CC=CC=2)=C(O)C=1C(C)=CC1=CC=CC=C1 JYLODCHTTBBBEF-UHFFFAOYSA-N 0.000 description 1
- DJRYJQNZAYJVGF-UHFFFAOYSA-N 4-methyl-2-(1-phenylethyl)phenol Chemical compound C=1C(C)=CC=C(O)C=1C(C)C1=CC=CC=C1 DJRYJQNZAYJVGF-UHFFFAOYSA-N 0.000 description 1
- KEUAFUBEAIPCIC-UHFFFAOYSA-N 4-methyl-2-(1-phenylprop-1-en-2-yl)phenol Chemical compound C=1C(C)=CC=C(O)C=1C(C)=CC1=CC=CC=C1 KEUAFUBEAIPCIC-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
- LKDKCTLTRLXBKU-UHFFFAOYSA-N C(CCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCC Chemical compound C(CCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCC LKDKCTLTRLXBKU-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000005749 Copper compound Substances 0.000 description 1
- 241000896693 Disa Species 0.000 description 1
- 101000889282 Homo sapiens Choline transporter-like protein 4 Proteins 0.000 description 1
- 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 1
- 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 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- 125000001204 arachidyl 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])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])[H] 0.000 description 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl 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])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])[H] 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 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
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000001196 nonadecyl 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])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])[H] 0.000 description 1
- 125000001117 oleyl 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])/C([H])=C([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])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical class C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004711 α-olefin 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
-
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- 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
- C10M2201/10—Compounds containing silicon
- C10M2201/1006—Compounds containing silicon 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
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
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- 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
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
-
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- 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
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
-
- 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
-
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- 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
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
-
- 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
- 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
- C10M2223/049—Phosphite
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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
- C10N2010/04—Groups 2 or 12
-
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- 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
-
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/065—Saturated Compounds
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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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy
Definitions
- This disclosure relates to an improvement in oxidation stability of lubricating oils by using a styrenated phenolic antioxidant and an optional synergistic secondary diarytemine.
- ZDDP zinc dialkyldithiophosphates
- a class of styrenated phenolic antioxidants offers superior antioxidancy and their mixtures with a secondary diarylamine exhibit synergistic effects and therefore are more effective than using either of the materials afone in inhibiting oxidation of lubricating oii compositions, in particular, the styrenated phenolics act synergistlcally with alkylated diarylamines to provide significant improvements in oxidation control.
- the present disclosure is directed to a lubricating oii composition comprising: (A) one or more base oils comprising API (American Petroleum Institute) Group I, Group M, Group ill, Group iV and synthetic lubricating base stocks of varying viscosity grades;
- R 1 and R 2 are independent and comprise hydrogen or styryl groups represented by the following formula (IA):
- n is an integer of from 0 to 5 and the ⁇ -position on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms, and R 3 is a hydrogen or hydrocarbyl group having from 1 to about 100 carbon atoms;
- At least one second antioxidant comprising one or more secondary diary Ia mines having the following general formula:
- Ar 1 and Ar 2 are independent and comprise aromatic hydrocarbons
- R 4 and Rs are independent and comprise hydrogen and hydrocarbyl groups
- a and b are independent and 0 to 3, with the proviso that (a+b) is not greater than 4.
- the present disclosure is directed to a method of increasing the oxidation stability of a lubricating oil, the method comprising: adding to a lubricating oil at least a first antioxidant comprising one or more hindered phenolic antioxidants represented by the general formula (I) and optionally, a second antioxidant comprising one or more secondary diarylamines represented by the general formula (II).
- hydrocarbyl as used herein includes hydrocarbon as well as substantially hydrocarbon groups.
- substantially hydrocarbon describes groups that contain heteroatom substituents that do not alter the predominantly hydrocarbon nature of the group.
- hydrocarbyl groups can include, but are not limited to, hydrocarbon substituents, substituted hydrocarbon substituents, and heteroatom substituents.
- Hydrocarbyl groups that may be utilized may contain from 1 to about 100 carbon atoms, preferably from about 6 to about 30 carbon atoms.
- Hydrocarbon substituents can include, but are not limited to aliphatic, such as a Iky I or alkenyl; alicyclic, such as cycioalkyl and cycioaikenyl; aromatic substituents; aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, and the like; as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical).
- Substituted hydrocarbon substituents comprising those substituents containing non-hydrocarbon portions which, in the context of this disclosure, do not alter the predominantly hydrocarbon nature of the substituent, those skilled in the art will be aware of such groups that can include, halo, hydroxy, mercapto, nitro, nitroso, sulfoxy, and cyano, for example.
- Heteroatom substituents for exampie, substituents that will, while having a predominantly hydrocarbon character within the context of this disclosure, contain at least one atom other than carbon present in a ring or chain otherwise composed of carbon atoms, such as alkoxy or alkylthio, for example.
- heteroatoms will be apparent to those of ordinary skill in the art and can include, for exampie, sulfur, oxygen, nitrogen, in addition to heteroatoms, substituents containing heteroatoms can be included, such as, pyridyl, furyl, thienyl, and imidazoiyl, for example.
- substituents containing heteroatoms can be included, such as, pyridyl, furyl, thienyl, and imidazoiyl, for example.
- no more than about 2, more preferably no more than one, s ⁇ bstit ⁇ ent containing a heteroatom will be present for every ten carbon atoms in the hydrocarbyl group. Most preferably, there will be no such heteroatom substituents in the hydrocarbyl group.
- the hindered phenolic for use as the first antioxidant in the practice of this disclosure can be represented by the following formula (I):
- Ri and Rz are independent and hydrogen or styryl groups represented by the following formula (IA):
- n an integer of from 0 to 5 and the exposition on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms; and R3 Is a hydrogen or hydrocarbyl group having from one to about 100 carbon atoms, preferably from one to about 40 carbon atoms.
- the optional second antioxidant comprising one or more secondary diarylamlnes can be represented as having the following general formula:
- the preferred aryl moieties suitable for the secondary diaryfamine as represented by the general formula (H) are phenyl or naphthyl.
- the hydrocarbyl moieties are alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyl, naphthyl, and naphthyl moieties that can be optionally substituted with alkyl, alkenyl , hydroxy!, and/or carboxyl groups, for example.
- hydrocarbyls suitable for the practice of this disclosure: (a) straight chain branched chain alkyl or aikenyl groups containing one to 40 carbon atoms, even more preferably straight chain or branched chain aikyl groups containing one to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, nonyl, decyt, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, nonadecyl, eicosyl, isomers and mixtures thereof and the like; (b) cyclic aikyl and alkenyl groups such as cyclopentyl,
- the hindered phenolic antioxidants represented by the formula (I) that are useful in the practice of this disclosure may include 2,6-bis(alpha- methylbenzyl)-4-methylphenol, 2,6-bis(alpha-methylbenzyl)-4-ethylphenol, 2,6-bis(alpha-methylbenzyl)-4-isobutylphenol,and the like; 2-alpha- methylbenzyl-4-methylphenol, 2-alpha-methylbenzyl-4-ethylphenol, 2-alpha- methylbenzyl-4-isobutylphenol, and the like; 2,6-bis(alpha-methylstyryl)-4- methylphenol, 2,6-bis(alpha-methylstyryl)-4-ethylphenol, 2,6-bis(alpha ⁇ methylstyryl)-4- ⁇ sobutylphenol, and the like; 2-aipha-methylstyryl-4- methylphenol, 2-alpha
- the secondary diary Ia mines represented by the general formulae ( II) that are useful in the practice of the present disclosure can include diphenylamine, monaikylated diphenylamine, dialkylated diphenylamine, trialkylated diphenylamine, and/or mixtures thereof, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine, mono- and/or di- butyldiphenylamine, mono- and/or di-octyldiphenylamine, mono- and/or di- nonyldiphenylamlne, phenyJ- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, diheptyldiphenylamine, mono- and/or di-( ⁇ -methylstyryl)diphenylamine, mono- and/or distyryidiphenylamine, 4-(p ⁇ toluenesulfonamido)diphenylamine,
- the antioxidants can be blended in the compositions in a range of about 0.01 to about 10 weight percent each, and preferably from about 0.1 to about 5 weight percent.
- the content ratio of the hindered phenolic antioxidant to the secondary diarylamine employed in the lubricating oil compositions of the present disclosure can be ⁇ n practically all proportions. In illustrative embodiments, the ratio will be in the range of 1 :99 to 99:1 parts by weight and more preferably, 90:10 to 10:90 parts by weight.
- the components (B) and (C) of the present disclosure can be pre-mixed according to the content ratio just defined then added to, or can be separately added to the lubricating oil (A) with the aid of mild heating (up to about 50°C) and mechanical agitation as needed.
- the antioxidants and the antioxidant mixtures of the present disciosure can be used in combination with other additives typically found in lubricating oils, as well as other antioxidants.
- the additives typically found in lubricating oils are, for example, dispersants, detergents, antiwear agents, antioxidants, friction modifiers, seal swell agents, demulsifiers, Vl (viscosity index) improvers, pour point depressants, antifoamants, corrosion inhibitors, and metal deactivators.
- Vl viscosity index
- pour point depressants antifoamants
- corrosion inhibitors and metal deactivators.
- Examples of dispersants can include polyisobutylene succ ⁇ nimldes, polyisobutylene succinate esters, and Mannich Base ashless dispersants.
- Examples of detergents can include metallic and ashless aikyl phenates, metallic and ashless s ⁇ lfu ⁇ zed alkyl phenates, metallic and ashless aikyl sulfonates, metallic and ashless alkyl salicylates, metallic and ashless saiigenin derivatives.
- antioxidants that can be used in combination with the antioxidant mixtures of the present disclosure can include dimethyl quinolines, trimethyfdihydroquinolines and oligomeric compositions derived therefrom, thiopropionates, metaiiic dithiocarbamates, oii soluble copper compounds, and para-phenylenediamines.
- An example of a more preferred substituted para- phenylenediamine is Naugalube ® 403 which is commercially available from Chemtura Corporation. ,
- anti-wear additives that can be used in combination with the additives of the present disclosure can include organoborates, organophosphites, organophosphates, organic sulfur-containing compounds, suifurized olefins, sulfurized fatty acid derivatives (esters), chlorinated paraffins, zinc dialkyldithiophosphates, zinc diaryldithiophosphates, dialkyldithiophosphate esters, diary I dithiophosphate esters, and phosphosulfurized hydrocarbons.
- Lubrizol® 677A Lubrizol 1095, Lubrizol 1097, Lubrizol 1360, L ⁇ brizol 1395, Lubrizol 5139, and Lubrizof 5604, among others; and from the Ciba Corporation: irgaiube® 62, irgai ⁇ be 211 , irgaiube 232, Irgai ⁇ be 349, Irgaiube 353, Irgaiube TPPT, Irgafos® OPH, among others; and from the Chemt ⁇ ra Corporation: Durad ® 40, Durad 48, D ⁇ rad 60, Durad 125, D ⁇ rad 220X, D ⁇ rad 110, O ⁇ rad 150, Durad 220, Durad 300, D ⁇ rad 150B, D ⁇ rad 220B, D ⁇ rad 620B, Durad 310M, Weston® 600, Weston DLP, and Nauga
- Examples of friction modifiers can include fatty acid esters and amides, organo moiybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum diafkyl dithiophosphates, molybdenum disulfide, tri-molybdenum cluster dialkyldithiocarbamates, and non-suifur molybdenum compounds, for example.
- molybdenum additives are commercially available from the R. T. Vanderbilt Company, Inc.: Molyvan® A, MoIy van L, Molyvan 807, Molyvan 856B, Molyvan 822, and Molyvan 855, among others.
- friction modifiers In addition to the aforementioned friction modifiers, the following are also examples of such additives and are commercially available from the Asahi Denka Kogyo K. K.: SAKURA-LUBE® 100, SAKURA-LUBE 165, SAKURA-LUBE 300, SAKURA- LUBE 310G, SAKURA-LUBE 321 , SAKURA-LUBE 474, SAKURA-LUBE 600, and SAKURA-LUBE 700, among others.
- the following are also examples of friction modifiers and are commercially available from Akzo Nobel Chemicals GmbH: Ketjen-Ox® 77M and Ketjen-Ox 77TS, among others. Naugalube® MoIyFM is also an example and is commercially available from the Chemtura Corporation.
- Vl Improvers can include olefin copolymers and dlsp ⁇ rsant olefin copolymers, for example.
- poiymethacrylate and equivalents thereof are examples of pour point depressants.
- polysiloxane and equivalents thereof can be employed as antifoamants.
- rust inhibitors can include polyoxyalkylene polyols, benzotriazole derivatives, and equivalents thereof.
- metal deactivators can include triazole, benzotriazole, 2- mercaptobenzothiazole, 2,5-dimercaptothiadiazole, tolyltrfazole derivatives, and N,N' ⁇ disa!icylidene ⁇ 1 ,2-dlaminopropane,
- compositions when they contain the aforementioned additives, are typically blended into at least one base oil in amounts effective to provide their normal attendant functions. Representative effective amounts of such additives are illustrated in Table 1. TABLE 1. Lubricant Composition
- Additive concentrates can comprise concentrated solutions or dispersions of the subject additives of this disclosure in amounts described above. These concentrates can comprise more than one additive and as such can be referred to as an additive-package. As an additive-package, several additives can be added simultaneously to the base oil to form the lubricating oil composition. Oissoiution of the additive concentrate into the lubricating oii can be facilitated by solvents and/or by mixing accompanied by mild heating. The concentrate or additive-package can be formutated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base oil.
- the subject additives of the present disclosure can be added to small amounts of base oil and/or compatible solvents along with other desirable additives to form additive-packages.
- These additive packages can contain active ingredients in collective amounts of from about 2.5 to about 90 percent, preferably from about 15 to about 75 percent, and more preferably from about 25 percent to about 60 percent by weight additives in the appropriate proportions with the remainder being base oil.
- the final formulations can employ from about 1 to 20 weight percent of the additive- package with the remainder comprising base oil.
- the total phosphorus content in the final formulations wili be less than about 600ppm.
- the additives of the present disclosure are useful in a variety of lubricating oil base stocks.
- the lubricating oil base stock is any natural or synthetic lubricating oil base stock fraction having a kinematic viscosity at 100 °C of about 2 to about 200 cSt, more preferably about 3 to about 150 cSt, and most preferably about 3 to about 100 cSt.
- the lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
- Suitable lubricating oil base stocks include base stocks obtained by isomerization of synthetic wax and wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude oil.
- Natural lubricating oils include animal oils, such as lard oil, tallow oil, vegetable oils including canoia oils, castor oils, and sunflower oils, for example, petroleum oils, mineral oils, and oils derived from coal or shale.
- Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpoiymerized olefins, gas-to- liquids prepared by Fischer-Tropsch technology, alkylbenzenes, polyphenyls, alkylated dipheny! ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, homologs, and the like.
- Synthetic lubricating oils also include aikylene oxide polymers, interpolymers, copolymers, and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, and etherification, for example.
- esters useful as synthetic oils comprises the esters of dicarboxytic acids with a variety of alcohols.
- Esters useful as synthetic oils also include those made from C 5 to C 18 monocarboxylic acids and polyols and polyoi ethers.
- Other esters useful as synthetic oils include those made from copolymers of ⁇ -olefins and dicarboxylic acids which are esterified with short or medium chain length alcohols.
- Silicon-based oils such as the polyalkyl-, polyarynl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils.
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, poly ⁇ -olefins, and the fike.
- the lubricating oil may be derived from unrefined, refined, re-refined oils, or mixtures thereof.
- Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar and bitumen) without further purification or treatment.
- Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
- Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to Improve one or more properties.
- Suitable purification techniques can include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, aii of which are well-known to those skilled in the art.
- Re-refined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
- Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
- Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
- the resulting Isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions having a specific viscosity range.
- Wax isomerate is also characterized by possessing very high viscosity indices, generally having a Vl of at least 130, preferably at least 135 or higher and, following dewaxing, a pour point of about -20 °C or lower.
- the lubricating oil used in the practice of the present disclosure can be selected from any of the base oils in Groups i-V as broadly specified in the American Petroleum Institute (API) Base OH lnterchangeabllity Guidelines.
- the five base oil groups are described in Table 2. TABLE 2.
- the additives of the present disclosure are especially useful as components in many different lubricating oil compositions.
- the additives can be included in a variety of oils with lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
- the additives can be included in crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines.
- the compositions can also be used in gas engine lubricants, steam and gas turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil and grease compositions.
- the low-phosphorous 5W2Q engine formulation was pre-blended using the following commercially available compositions. There is no particular restriction on the type and exact composition of the materials in the context of the present disclosure.
- the Mid-High Temperature Thermo-oxidative Engine Oil Simulation Test was performed according to the ASTM D7097 standard procedure to determine the deposit forming tendencies of the engine oil.
- TEOST determines the mass of deposit formed on a specially constructed steel rod by continuously stressing a repetitive passage of 8.5 ml of test oil under thermai-oxidative and catalytic conditions for 24 hours. The less the amount of deposits obtained, the better the oxidation stability of the oil. Throughout the 24 hour test duration, volatile compounds of the test oil that are there originally or formed because of the oxidation of the oil are also collected in a small vial by means of condensation. Table 6 summarizes the test conditions.
- Rotating Pressure Vessel Oxidation Test was conducted according to the standard test method specified by ASTM D 2272.
- the RPVOT utilizes an oxygen-pressured vessel to evaluate the oxidation stability of new and in service turbine oils, having the same composition (base stock and additives), in the presence of water and a copper catalyst coil at 150°C.
- the test oil, water, and a copper catalyst coil which are separately contained in a covered glass container, are placed.
- the vessel is charged with oxygen to a pressure of 90 psi and placed in a constant temperature oil bath set at 150°C, and rotated axially at 100 rpm at an angle of 30 degrees from the horizontal.
- the number of minutes required to reach a specific drop 25 psi in gage pressure indicates the oxidation stability of the test sample. The longer the duration to reachth ⁇ required pressure drop, the better oxidative stability of the test sample.
- Table 10 lists the RPVOT test conditions.
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Abstract
Compositions are disclosed that comprise a lubricant, at least a first antioxidant and an optional second antioxidant, the first antioxidant being a styrenated phenolic antioxidant and the optional second antioxidant a secondary diarylamine for synergistic antioxidant action. Also disclosed is a method of increasing the oxidation stability of lubricating oils comprising: adding thereto at least a first antioxidant and, optionally, a second antioxidant, the first antioxidant being a styrenated phenolic antioxidant and the optional second antioxidant a secondary diarylamine.
Description
LUBRICANT COMPOSITIONS STABILIZED WITH STYRENATED PHENOLIC ANTIOXIDANT
TECHNICAL FIELD
[0001] This disclosure relates to an improvement in oxidation stability of lubricating oils by using a styrenated phenolic antioxidant and an optional synergistic secondary diarytemine.
BACKGROUND OF THE DISCLOSURE
[0002] Hydrocarbon based lubricants, when exposed to heat and oxygen (air) that are ubiquitously present during their manufacture, transport, storage, or use, will oxidize over time. Uncontrolled oil oxidation produces harmful species, which eventually compromises the designated functions of the lubricant, decreases the service life, and, to a greater extent, damages the machinery it lubricates. One practical approach to the prevention of lubricant oxidation is the employment of a suitable antioxidant system comprising one or more active components.
[0003] Driven by escalating performance and environmental requirements for many classes of lubricant products, the industry is continuously looking for high performance antioxidants to work with modem lubricant formulations to achieve, among other things, increased oxidative stability and drain intervals, improved tow temperature properties, and greater fuel economy. One notable
change from the lubricant formulation point of view is the reduction in the use of zinc dialkyldithiophosphates (ZDDP). Over the past decades, ZDDP's have been an important class of lubricant additive for many types of lubricants owing to their superior cost-effectiveness in wear protection and oxidation inhibition, particularly through a synergistic action with primary antioxidants. However, the presence of zinc contributes to the formation of ash particulates and volatile phosphors, that after entering the exhaust stream, poison the NOx catalysis, thus shortening the useful iife of a catalytic converter.
[0004] In view of the aforementioned shortcomings of the known zinc and phosphorus-comprising additives, efforts have been made to provide lubricating oil additives that contain neither zinc nor phosphorus or, at least, contain them in substantially reduced amounts. It would therefore be desirable to provide improved additives for stabilizing and/or inhibiting lubricating oils from oxidative, thermal, and/or light-induced degradation while reducing the content of zinc and phosphorous employed In the lubricating oils.
[0005] According to the present disclosure, we have discovered an effective phenolic antioxidant that offers superior antioxidancy on its own and possesses unique antioxidant synergy when properiy used in combination with a secondary diary Ia mine antioxidant for lubricant base stocks and/or lubricant formulations, particularly in those containing a low level of ZDDP.
SUMMARY OF THE DISCLOSURE
[0006] it has now been discovered that a class of styrenated phenolic antioxidants offers superior antioxidancy and their mixtures with a secondary diarylamine exhibit synergistic effects and therefore are more effective than using either of the materials afone in inhibiting oxidation of lubricating oii compositions, in particular, the styrenated phenolics act synergistlcally with alkylated diarylamines to provide significant improvements in oxidation control. More particularly, the present disclosure is directed to a lubricating oii composition comprising: (A) one or more base oils comprising API (American Petroleum Institute) Group I, Group M, Group ill, Group iV and synthetic lubricating base stocks of varying viscosity grades;
(B) at least a first antioxidant selected from one or more hindered phenolics or an isomer or isomeric mixture thereof having the following general formula:
wherein R1 and R2 are independent and comprise hydrogen or styryl groups represented by the following formula (IA):
wherein n is an integer of from 0 to 5 and the α-position on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms, and R3 is a hydrogen or hydrocarbyl group having from 1 to about 100 carbon atoms; and
(C) optionally, at least one second antioxidant comprising one or more secondary diary Ia mines having the following general formula:
(R4)a-Ar1-NH-Ar2-(R5)b (II)
wherein Ar1 and Ar2 are independent and comprise aromatic hydrocarbons, R4 and Rs are independent and comprise hydrogen and hydrocarbyl groups and a and b are independent and 0 to 3, with the proviso that (a+b) is not greater than 4.
[0007] In another aspect, the present disclosure is directed to a method of increasing the oxidation stability of a lubricating oil, the method comprising: adding to a lubricating oil at least a first antioxidant comprising one or more hindered phenolic antioxidants represented by the general formula (I) and
optionally, a second antioxidant comprising one or more secondary diarylamines represented by the general formula (II).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0008] The term "hydrocarbyl" as used herein includes hydrocarbon as well as substantially hydrocarbon groups. "Substantially hydrocarbon" describes groups that contain heteroatom substituents that do not alter the predominantly hydrocarbon nature of the group. Examples of hydrocarbyl groups can include, but are not limited to, hydrocarbon substituents, substituted hydrocarbon substituents, and heteroatom substituents. Hydrocarbyl groups that may be utilized may contain from 1 to about 100 carbon atoms, preferably from about 6 to about 30 carbon atoms. [0009] Hydrocarbon substituents can include, but are not limited to aliphatic, such as a Iky I or alkenyl; alicyclic, such as cycioalkyl and cycioaikenyl; aromatic substituents; aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, and the like; as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical). [0010] Substituted hydrocarbon substituents, comprising those substituents containing non-hydrocarbon portions which, in the context of this disclosure, do not alter the predominantly hydrocarbon nature of the substituent, those
skilled in the art will be aware of such groups that can include, halo, hydroxy, mercapto, nitro, nitroso, sulfoxy, and cyano, for example. [0011] Heteroatom substituents, for exampie, substituents that will, while having a predominantly hydrocarbon character within the context of this disclosure, contain at least one atom other than carbon present in a ring or chain otherwise composed of carbon atoms, such as alkoxy or alkylthio, for example. Suitable heteroatoms will be apparent to those of ordinary skill in the art and can include, for exampie, sulfur, oxygen, nitrogen, in addition to heteroatoms, substituents containing heteroatoms can be included, such as, pyridyl, furyl, thienyl, and imidazoiyl, for example. Preferably, no more than about 2, more preferably no more than one, sυbstitυent containing a heteroatom will be present for every ten carbon atoms in the hydrocarbyl group. Most preferably, there will be no such heteroatom substituents in the hydrocarbyl group.
[0012] As stated above, the hindered phenolic for use as the first antioxidant in the practice of this disclosure can be represented by the following formula (I):
wherein Ri and Rz are independent and hydrogen or styryl groups represented by the following formula (IA):
wherein n Is an integer of from 0 to 5 and the exposition on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms; and R3 Is a hydrogen or hydrocarbyl group having from one to about 100 carbon atoms, preferably from one to about 40 carbon atoms. The optional second antioxidant comprising one or more secondary diarylamlnes can be represented as having the following general formula:
(R4)a-Ar1-NH-Ar2-(R5)b (II) wherein Ari and Ar2 are independent and comprise aromatic hydrocarbons, and R4 and R5 are independent and comprise hydrogen and hydrocarbyl groups, and a and b are independent and 0 to 3, with the proviso that (a+b) is not greater than 4. The preferred aryl moieties suitable for the secondary
diaryfamine as represented by the general formula (H) are phenyl or naphthyl. There is no particular restriction on the type and total number of carbon atoms In the hydrocarbyl group, R3 to R5, of the hindered phenolics and the substituted secondary diarylamines as represented by the general formulae (I) - (II), respectively, with the proviso that the total number of carbon atoms render sufficient thermal stabilities and solubility of the additives in the base oil (A). Preferably, the hydrocarbyl moieties are alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyl, naphthyl, and naphthyl moieties that can be optionally substituted with alkyl, alkenyl , hydroxy!, and/or carboxyl groups, for example. The following are examples of preferred hydrocarbyls suitable for the practice of this disclosure: (a) straight chain branched chain alkyl or aikenyl groups containing one to 40 carbon atoms, even more preferably straight chain or branched chain aikyl groups containing one to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, nonyl, decyt, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, nonadecyl, eicosyl, isomers and mixtures thereof and the like; (b) cyclic aikyl and alkenyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclododecenyl, cyclopentadienyl, cydohexadienyl, cycloheptadienyl, cyclooctadienyl, and the like wrth optionally substituted with one or more alkyl or alkenyl radicals having one to 40 carbon atoms, and more preferably one to 16 carbon atoms suGh as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, isomers and mixtures of the foregoing, and the like; (c) phenyl, phenyl substituted with one or more alkyl or alkenyl radicals having one to 40 carbon atoms, and even more preferably one to 16 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadeyl, hexadecyl, Isomers of the foregoing, and the like; (d) naphthyl and naphthyl substituted with one or more aikyl or alkenyl radicals having one to 40 carbon atoms, and even more preferably one to 16 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadeyl, hexadecyl, isomers and mixtures thereofof the foregoing, and the like; (e) heteroatom substituents, particularly alkoxyaikyl, alkoxyary! groups having from one to 40 carbon atoms, and more preferably from one to 20 carbon atoms such as methoxymethyl, ethoxymethyl, ethoxyethyl, pro poxym ethyl, propoxyethyl, propoxypropyl, and the like; and phenyl substituted with one or more alkoxy groups having one to 16 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, tridecyl, tetradecyl, pentadeyl, hexadecyl isomers and mixtures of the foregoing, and the like; (f) substituted hydrocarbon substituents, particularly hydroxyl, carboxyl, nitro, or cyano, for example,
[0013] With wide variation in the composition of the hydrocarbyl moieties, the hindered phenolic antioxidants represented by the formula (I) that are useful in the practice of this disclosure may include 2,6-bis(alpha-
methylbenzyl)-4-methylphenol, 2,6-bis(alpha-methylbenzyl)-4-ethylphenol, 2,6-bis(alpha-methylbenzyl)-4-isobutylphenol,and the like; 2-alpha- methylbenzyl-4-methylphenol, 2-alpha-methylbenzyl-4-ethylphenol, 2-alpha- methylbenzyl-4-isobutylphenol, and the like; 2,6-bis(alpha-methylstyryl)-4- methylphenol, 2,6-bis(alpha-methylstyryl)-4-ethylphenol, 2,6-bis(alpha~ methylstyryl)-4-ϊsobutylphenol, and the like; 2-aipha-methylstyryl-4- methylphenol, 2-alpha«methylstyryf-4-ethylphenof, 2~alpha-methylstyryl-4- isobυtylphenol, and the like; 2,2'-thiobis(6-alpha-methylbenzyl-4- methylphenol), 4,4'-thiobis(2,6-di-alpha-methylbenzyl-4-methylphenol), and the like; 2,2'-thiobis(6-aJpha-methylstyryl-4-methylphenol), 4,4'-thiobis(2,6-di- aipha-methylstyryl-4-methylphenoi), and the iike; 2,2'-methylenebis(6~alpha- methylbenzyl-4-methylphenol), 4,4'-methyIenebis(2,6-di-alpha-methylbenzyl-4- methyfphenol), and the like; 2,2"-methylenebis(6-alpha-methylstyryl-4- methylphenol), and 4,4'-methylenebis(2,e-di-alpha-methylstyryl-4- methylphenoi), for example.
[0014] According to an embodiment, the secondary diary Ia mines represented by the general formulae ( II) that are useful in the practice of the present disclosure can include diphenylamine, monaikylated diphenylamine, dialkylated diphenylamine, trialkylated diphenylamine, and/or mixtures thereof, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine, mono- and/or di- butyldiphenylamine, mono- and/or di-octyldiphenylamine, mono- and/or di-
nonyldiphenylamlne, phenyJ-α-naphthylamine, phenyl-β-naphthylamine, diheptyldiphenylamine, mono- and/or di-(α-methylstyryl)diphenylamine, mono- and/or distyryidiphenylamine, 4-(p~toluenesulfonamido)diphenylamine, 4- isopropoxydiphenylamine, f-octylated N-phenyl-1-πaphthylamine, mixtures of mono- and dialkylated t-butyl-t-octyldiphenylamines. The following are examples of preferred secondary diarylamines that are commercially available from the Ciba Coφoration: Irganox® L67, Irganox L57, and Irganox L06. The following are examples of more preferred secondary diarylamines and are commercially available from the Chemtura Corporation: Naugalube® 438, Naugaiube 438L, Naυgalube 690, Naugalυbe 640, Naugalube 635, Naυgalube 680, Naugaiube AMS, Naugalube APAN, and Naugard PANA.
[0015] in the preparation of the lubricating oil compositions comprising component (B), the hindered phenolic antioxidant of the above general formulae (I), and the component (C), the secondary diarylamine with the above general formula (II), the antioxidants can be blended in the compositions in a range of about 0.01 to about 10 weight percent each, and preferably from about 0.1 to about 5 weight percent. The content ratio of the hindered phenolic antioxidant to the secondary diarylamine employed in the lubricating oil compositions of the present disclosure can be \n practically all proportions. In illustrative embodiments, the ratio will be in the range of 1 :99 to 99:1 parts by weight and more preferably, 90:10 to 10:90 parts by weight. The components
(B) and (C) of the present disclosure can be pre-mixed according to the content ratio just defined then added to, or can be separately added to the lubricating oil (A) with the aid of mild heating (up to about 50°C) and mechanical agitation as needed.
[0016] The antioxidants and the antioxidant mixtures of the present disciosure can be used in combination with other additives typically found in lubricating oils, as well as other antioxidants. The additives typically found in lubricating oils are, for example, dispersants, detergents, antiwear agents, antioxidants, friction modifiers, seal swell agents, demulsifiers, Vl (viscosity index) improvers, pour point depressants, antifoamants, corrosion inhibitors, and metal deactivators. Such additives are well known to those skilled in the art and there is no particular restriction on the type of these additives for this disclosure. U.S. Pat. No. 5,498,809, incorporated herein by reference in its entirety, discloses useful lubricating oil composition additives.
[0017] Examples of dispersants can include polyisobutylene succϊnimldes, polyisobutylene succinate esters, and Mannich Base ashless dispersants. Examples of detergents can include metallic and ashless aikyl phenates, metallic and ashless sυlfuπzed alkyl phenates, metallic and ashless aikyl sulfonates, metallic and ashless alkyl salicylates, metallic and ashless saiigenin derivatives.
[0018] Examples of antioxidants that can be used in combination with the antioxidant mixtures of the present disclosure can include dimethyl quinolines, trimethyfdihydroquinolines and oligomeric compositions derived therefrom, thiopropionates, metaiiic dithiocarbamates, oii soluble copper compounds, and para-phenylenediamines. The following are examples of preferred substituted para-phenylenediamines that are commercially available from the Flβxsys Corporation: Santoflex® IPPD1 Santoflex 6PPD, Santoflex 44PD, Santoflex 77PD, Santoflex 134PD, Santofiex 1350PD, Santoflex 715PD, and Santoflex 434PD. An example of a more preferred substituted para- phenylenediamine is Naugalube® 403 which is commercially available from Chemtura Corporation. ,
[0019] Examples of anti-wear additives that can be used in combination with the additives of the present disclosure can include organoborates, organophosphites, organophosphates, organic sulfur-containing compounds, suifurized olefins, sulfurized fatty acid derivatives (esters), chlorinated paraffins, zinc dialkyldithiophosphates, zinc diaryldithiophosphates, dialkyldithiophosphate esters, diary I dithiophosphate esters, and phosphosulfurized hydrocarbons. The following are examples of the aforementioned additives and are commercially available from the Lubrizol Corporation: Lubrizol® 677A, Lubrizol 1095, Lubrizol 1097, Lubrizol 1360,
Lυbrizol 1395, Lubrizol 5139, and Lubrizof 5604, among others; and from the Ciba Corporation: irgaiube® 62, irgaiυbe 211 , irgaiube 232, Irgaiυbe 349, Irgaiube 353, Irgaiube TPPT, Irgafos® OPH, among others; and from the Chemtυra Corporation: Durad® 40, Durad 48, Dυrad 60, Durad 125, Dυrad 220X, Dυrad 110, Oυrad 150, Durad 220, Durad 300, Dυrad 150B, Dυrad 220B, Dυrad 620B, Durad 310M, Weston® 600, Weston DLP, and Naugatube® TPP.
[0020] Examples of friction modifiers can include fatty acid esters and amides, organo moiybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum diafkyl dithiophosphates, molybdenum disulfide, tri-molybdenum cluster dialkyldithiocarbamates, and non-suifur molybdenum compounds, for example. The following are examples of molybdenum additives and are commercially available from the R. T. Vanderbilt Company, Inc.: Molyvan® A, MoIy van L, Molyvan 807, Molyvan 856B, Molyvan 822, and Molyvan 855, among others. In addition to the aforementioned friction modifiers, the following are also examples of such additives and are commercially available from the Asahi Denka Kogyo K. K.: SAKURA-LUBE® 100, SAKURA-LUBE 165, SAKURA-LUBE 300, SAKURA- LUBE 310G, SAKURA-LUBE 321 , SAKURA-LUBE 474, SAKURA-LUBE 600, and SAKURA-LUBE 700, among others. The following are also examples of friction modifiers and are commercially available from Akzo Nobel Chemicals
GmbH: Ketjen-Ox® 77M and Ketjen-Ox 77TS, among others. Naugalube® MoIyFM is also an example and is commercially available from the Chemtura Corporation.
[0021] Examples of Vl Improvers can include olefin copolymers and dlspβrsant olefin copolymers, for example. In certain embodiments, poiymethacrylate and equivalents thereof are examples of pour point depressants. In another embodiment, polysiloxane and equivalents thereof can be employed as antifoamants. Examples of rust inhibitors can include polyoxyalkylene polyols, benzotriazole derivatives, and equivalents thereof. Examples of metal deactivators can include triazole, benzotriazole, 2- mercaptobenzothiazole, 2,5-dimercaptothiadiazole, tolyltrfazole derivatives, and N,N'~disa!icylidene~1 ,2-dlaminopropane, The following are examples of metal deactivators and are commercially available from Ciba Corporation: Irgamet® 30, lrgamet 39 and irgamet 42.
Lubricant Compositions
[0022] Compositions, when they contain the aforementioned additives, are typically blended into at least one base oil in amounts effective to provide their normal attendant functions. Representative effective amounts of such additives are illustrated in Table 1.
TABLE 1. Lubricant Composition
[0023] Additional additives can be employed and in such cases it may be desirable, although not necessary, to prepare additive concentrates. Additive concentrates can comprise concentrated solutions or dispersions of the subject additives of this disclosure in amounts described above. These concentrates can comprise more than one additive and as such can be referred to as an additive-package. As an additive-package, several additives can be added simultaneously to the base oil to form the lubricating oil composition. Oissoiution of the additive concentrate into the lubricating oii can be facilitated by solvents and/or by mixing accompanied by mild heating. The concentrate or additive-package can be formutated to contain the additives in
proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base oil. Thus, the subject additives of the present disclosure can be added to small amounts of base oil and/or compatible solvents along with other desirable additives to form additive-packages. These additive packages can contain active ingredients in collective amounts of from about 2.5 to about 90 percent, preferably from about 15 to about 75 percent, and more preferably from about 25 percent to about 60 percent by weight additives in the appropriate proportions with the remainder being base oil. The final formulations can employ from about 1 to 20 weight percent of the additive- package with the remainder comprising base oil. Preferably, the total phosphorus content in the final formulations wili be less than about 600ppm.
[0024] All of the weight percentages expressed herein (unless otherwise indicated) are based on the active ingredient (Al) content of the additive, and/or upon the total weight of any additive-package, or formulation, which will be the sum of the Al weight of each additive plus the weight of total oil or diluent.
[0025] In general, the additives of the present disclosure are useful in a variety of lubricating oil base stocks. The lubricating oil base stock is any natural or synthetic lubricating oil base stock fraction having a kinematic
viscosity at 100 °C of about 2 to about 200 cSt, more preferably about 3 to about 150 cSt, and most preferably about 3 to about 100 cSt. The lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. Suitable lubricating oil base stocks include base stocks obtained by isomerization of synthetic wax and wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude oil. Natural lubricating oils include animal oils, such as lard oil, tallow oil, vegetable oils including canoia oils, castor oils, and sunflower oils, for example, petroleum oils, mineral oils, and oils derived from coal or shale.
[0026] Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpoiymerized olefins, gas-to- liquids prepared by Fischer-Tropsch technology, alkylbenzenes, polyphenyls, alkylated dipheny! ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, homologs, and the like. Synthetic lubricating oils also include aikylene oxide polymers, interpolymers, copolymers, and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, and etherification, for example.
[0027] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxytic acids with a variety of alcohols. Esters useful as
synthetic oils also include those made from C5 to C18 monocarboxylic acids and polyols and polyoi ethers. Other esters useful as synthetic oils include those made from copolymers of α-olefins and dicarboxylic acids which are esterified with short or medium chain length alcohols.
[0028] Silicon-based oils, such as the polyalkyl-, polyarynl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, poly α-olefins, and the fike.
[0029] The lubricating oil may be derived from unrefined, refined, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar and bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to Improve one or more properties. Suitable purification techniques can include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, aii of which are
well-known to those skilled in the art. Re-refined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
[0030] Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst. Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process. The resulting Isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions having a specific viscosity range. Wax isomerate is also characterized by possessing very high viscosity indices, generally having a Vl of at least 130, preferably at least 135 or higher and, following dewaxing, a pour point of about -20 °C or lower.
[0031] The lubricating oil used in the practice of the present disclosure can be selected from any of the base oils in Groups i-V as broadly specified in the
American Petroleum Institute (API) Base OH lnterchangeabllity Guidelines. The five base oil groups are described in Table 2. TABLE 2. API Base OH Category
[0032] The additives of the present disclosure are especially useful as components in many different lubricating oil compositions. The additives can be included in a variety of oils with lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. The additives can be included in crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines. The compositions can also be used in gas engine lubricants, steam and gas turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil and grease compositions.
[0033] The advantages and the important features of the present disclosure will be demonstrated in the following examples.
EXAMPLE 1
[0034] The antioxidant efficacy of the hindered phenolic and the synergistic effects; from a combined usage of the hindered phenoiic and the secondary diarylamine, have been demonstrated in a iow-phosphorus 5W20 engine oil formulation by using the pressurized differential scanning calorimetry (PDSC) test and the Mid-High Temperature Thermo-oxidation Engine Oil Simulation Test (TEOST, MHT).
[0035] Preparation of a Low-Phosphorus 5W20 Engine Oil Formulation
The low-phosphorous 5W2Q engine formulation was pre-blended using the following commercially available compositions. There is no particular restriction on the type and exact composition of the materials in the context of the present disclosure.
TABLE 3. Low- hos horus 5W20 En ine Oil Pre-blend
[0036] To the 5W20 engine oil pre-blend set forth in Table 3 was added antioxidants, as depicted in Tables 5 and 7 below, in preparation of 5W20 engine oils. The finished engine oils contain approximately 450 ppm of phosphorus derived from (ZDDP).
Pressurized Differential Scanning Calorimetrv Results [0037] The Pressurized Differential Scanning Calorimetry (PDSC) measures the oxidation induction time (OtT) of oil. The instrument used is a Mettler® DSC27HP manufactured by Mettler-Toledo, lnc (Switzerland). The instrument has a typical repeatability of ±2.5 minutes with 95 percent confidence over an OIT of 100 minutes. The PDSC test conditions are given in Table 4. For every 50 grams of test biend prepared, 40 μi of oii soluble ferric naphthenate (6 weight percent in mineral oil) was added, prior to PDSC testing, to facilitate 50 ppm of iron in oil. At the beginning of a PDSC run, the steel cell is pressurized with oxygen and heated at a rate of 40°C per minute to the prescribed isothermal temperature. The induction time is measured from the time the sample reaches its isothermal temperature until the enthalpy change is observed. The longer the oxidation induction time, the better the oxidation stability of the oil
TABLE 4. PDSC Test Conditions
[0038] The finished 5W20 engine oils were tested in the PDSC using the conditions set forth in Table 4. The test results in terms of average OiT and
standard deviation of each duplicate run are given in Table 5 below. The exceedingly long OiT results of blends 1 and 3 in the data table as compared to the respective comparatives demonstrate that the engine oil compositions containing the hindered phenolic antioxidant of the present disclosure have superior oxidative stabilities.
TABLE 5. PDSC Results of the 5W20 Engine Oil Blends Containing a Single Antioxidant.
Mid-High Temperature Thermo-oxidative Engine Oil Simulation Test [0039] The Mid-High Temperature Thermo-oxidative Engine Oil Simulation Test (MHT TEOST) was performed according to the ASTM D7097 standard procedure to determine the deposit forming tendencies of the engine oil. TEOST determines the mass of deposit formed on a specially constructed steel rod by continuously stressing a repetitive passage of 8.5 ml of test oil under thermai-oxidative and catalytic conditions for 24 hours. The less the amount of deposits obtained, the better the oxidation stability of the oil.
Throughout the 24 hour test duration, volatile compounds of the test oil that are there originally or formed because of the oxidation of the oil are also collected in a small vial by means of condensation. Table 6 summarizes the test conditions.
TABLE 6, TEOST MHT Test Conditions ASTM D 7097
[0040] The results obtained from the TEOST testing of the finished 5W20 engine oils are given in Table 7. Based on the data, the improved deposit control efficacy of the additives of this disclosure has been clearly demonstrated. The significantly lower amounts of deposits obtained for blends 6 and 7 as compared to that of the blend 5, the pre-blend, and compared to the comparative blends 8 and 9 respectively containing an equal level of a commercial hindered phenolic ester antioxidant demonstrate that the lubricating oil compositions containing the antioxidant of this disclosure have superior oxidative stability to better control deposit formation in the TEOST.
TABLE 7. TEOST Results of the 5W20 Engine Oil Blends Containing a Single Antioxidant
[0041] In the TEOST, the synergistic antioxidant effect from a proper mixing of the styrenated phenolics and a secondary diarylamine according to the practice of this disclosure in stabilizing the 5W20 engine oil formulation is more clearly seen. As indicated by the data tabulated in Table 8, the lower amounts of deposits obtained for blends 10 and 11 demonstrate that the lubricating oils containing appropriate mixtures of the antioxidant mixtures according to the present disclosure have superior oxidative stability to better control deposit formation in the TEOST.
TABLE 8. TEOST Results of the 5W20 Engine Oil Blends Containing Multiple Antioxidants
EXAMPLE 2
[0042] The antioxidant efficacy of the hindered phenolic and the synergistic effects from a combined usage of the hindered phenolic and the secondary diarylamine according to the practice of this disclosure have been demonstrated in an industrial turbine oil formulation, tested by using the Rotating Pressure Vessel Oxidation Test (RPVOT) method.
Preparation of an Industrial Turbine Formulation
[0043] An industrial turbine oil pre-btend was first prepared with the following commercially available components. There is no particular restriction on the type and exact composition of the materials in the context of the present disclosure.
TABLE 9. Turbine Oil Pre-blend
[0044] To the turbine oii pre-blend as set forth in Table 9 was added an antioxidant as depicted in Table 11 in preparation of a variety of fully formulated industrial turbine oils each containing 1.0 percent by weight of antioxidants in total.
Rotating Pressure Vessel Oxidation Test (RPVOT) [0045] The Rotating Pressure Vessel Oxidation Test (RPVOT) was conducted according to the standard test method specified by ASTM D 2272. The RPVOT utilizes an oxygen-pressured vessel to evaluate the oxidation stability of new and in service turbine oils, having the same composition (base stock and additives), in the presence of water and a copper catalyst coil at 150°C. In a vessel equipped with a pressure gauge, the test oil, water, and a copper catalyst coil, which are separately contained in a covered glass container, are placed. The vessel is charged with oxygen to a pressure of 90 psi and placed in a constant temperature oil bath set at 150°C, and rotated axially at 100 rpm at an angle of 30 degrees from the horizontal. The number of minutes required to reach a specific drop 25 psi in gage pressure indicates the oxidation stability of the test sample. The longer the duration to reachthβ
required pressure drop, the better oxidative stability of the test sample. Table 10 lists the RPVOT test conditions.
TABLE 10, RPVOT Test Conditions
[0046] The RPVOT test results of the turbine oHs are set forth in Table 11. It can be seen from the above data that the turbine oil formulation containing the styrenated phenolic antioxidant (btend 17) of the present disclosure possessed better oxidative stability than the turbine oii pre-blend (blend 15) and the comparative biend 20 containing an equal amount of hindered phenolic ester. It can also be seen from the above data that the turbine oil formulation containing a proper mixture of the styrenated phenolic antioxidant and the secondary diarylamine (biend 19) according to the practice of the presentation disclosure exhibited a synergy that better stabilized the turbine oii.
TABLE 11. RPVOT Results of the Turbine Oils
[0047] in view of the many changes and modifications that can be made without departing from principles underlying the present disclosure, reference should be made to the appended claims for an understanding of the scope of the protection to be afforded the disclosure.
Claims
1. A composition comprising: (a) at least one lubricating oil comprising one or more Group I, Group H, Group IiI, Group IV or synthetic lubricating base stocks of varying viscosity grades; (b) at least a first antioxidant comprising one or more hindered phenolics having the general formula:
or an Isomer or isomeric mixture thereof wherein Ri and R2 are independent and hydrogen or styryl groups represented by formula (IA):
wherein n is an integer of from 0 to 5 and the α-position on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms; and R3 is hydrogen or a hydrocarbyl group; and (c) an optional second antioxidant comprising one or more secondary dlarylamines having the general formula: (R4)a-Ar1-NH-Ar2-(R5)b wherein Ar1 and Ar2 are independent and comprise one or more aromatic hydrocarbons, and R4 and R5 are independent and comprise one or more hydrogen or hydrocarbyl groups, , and a and b are independent and integers from 0 to 3, with the proviso that (a+b) is not greater than 4.
2. A composition of claim 1 further comprising at least one additional additive comprising one or more dispersants, detergents, rust inhibitors, metal deactivators, antiwear agents, antifoamants, friction modifiers, seal swell agents, demulsifiers, viscosity index Improvers, and pour point depressants.
3. A composition of claim 1 wherein the lubricant is suitable for use in a high temperature and iron cataiyzed environment,
4. A composition of claim 3 wherein the lubricant is a grease.
5. A method of increasing the oxidation stability of a lubricating oil comprising one or more Group I, Group II, Group III, Group IV or synthetic lubricating base stocks of varying viscosity grades comprising adding thereto a composition comprising from about 0.01 to about 10 weight percent of a first antioxidant and from about 0.01 to about 10 weight percent of a second antioxidant, the first antioxidant comprising one or more hindered phenoitcs having the general formula:
or an isomer or isomeric mixture thereof wherein Ri and R2 are independent and hydrogen or styryl groups represented by formula (IA):
wherein n Is an integer of from 0 to 5 and the α-position on the styryl group is optionally substituted with a hydrocarbyl group having from 1 to about 8 carbon atoms; and R3 is hydrogen or a hydrocarbyl group and the second antioxidant comprising one or more secondary diarylamines having the general formula: (R4)s-Arr NH-Ar2-(R5)b wherein Ari and Ar2 are independent and comprise one or more aromatic hydrocarbons, and R4 and R5 are Independent and comprise one or more hydrogen or hydrocarbyl groups , and a and b are independent and integers from 0 to 3, with the proviso that (a+b) is not greater than 4.
6. The method of claim 5 wherein the content ratio of the first antioxidant to the second antioxidant is from 1 :99 to 99:1.
7. The method of claim 5 further comprising one or more dispersants, detergents, rust inhibitors, metal deactivators, antiwear agents, antifoamants, friction modifiers, sea! swell agents, demulsifters, viscosity index improvers, and pour point depressants.
8. A method of claim 5 wherein the composition comprises about 600 ppm or less of phosphorus.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/825,449 US20090011961A1 (en) | 2007-07-06 | 2007-07-06 | Lubricant compositions stabilized with styrenated phenolic antioxidant |
| PCT/US2008/068105 WO2009009293A1 (en) | 2007-07-06 | 2008-06-25 | Lubricant compositions stabilized with styrenated phenolic antioxidant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2162518A1 true EP2162518A1 (en) | 2010-03-17 |
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| EP08771877A Withdrawn EP2162518A1 (en) | 2007-07-06 | 2008-06-25 | Lubricant compositions stabilized with styrenated phenolic antioxidant |
| EP08781436A Withdrawn EP2164933A2 (en) | 2007-07-06 | 2008-07-07 | Liquid styrenated phenolic compositions and processes for forming same |
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| EP (2) | EP2162518A1 (en) |
| JP (2) | JP2010532414A (en) |
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| CN (2) | CN101688142A (en) |
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| WO (2) | WO2009009293A1 (en) |
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- 2007-07-06 US US11/825,449 patent/US20090011961A1/en not_active Abandoned
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2008
- 2008-06-25 JP JP2010515051A patent/JP2010532414A/en active Pending
- 2008-06-25 KR KR1020107000219A patent/KR20100029119A/en not_active Withdrawn
- 2008-06-25 RU RU2010103963/04A patent/RU2010103963A/en not_active Application Discontinuation
- 2008-06-25 EP EP08771877A patent/EP2162518A1/en not_active Withdrawn
- 2008-06-25 CN CN200880021556A patent/CN101688142A/en active Pending
- 2008-06-25 WO PCT/US2008/068105 patent/WO2009009293A1/en not_active Ceased
- 2008-07-07 EP EP08781436A patent/EP2164933A2/en not_active Withdrawn
- 2008-07-07 KR KR1020107000222A patent/KR20100029120A/en not_active Withdrawn
- 2008-07-07 CN CN200880023567A patent/CN101688143A/en active Pending
- 2008-07-07 RU RU2010103965/04A patent/RU2470067C2/en not_active IP Right Cessation
- 2008-07-07 WO PCT/US2008/069320 patent/WO2009009481A2/en not_active Ceased
- 2008-07-07 JP JP2010515283A patent/JP2010532763A/en active Pending
Non-Patent Citations (1)
| Title |
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| See references of WO2009009293A1 * |
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| CN101688143A (en) | 2010-03-31 |
| EP2164933A2 (en) | 2010-03-24 |
| US20090011961A1 (en) | 2009-01-08 |
| JP2010532414A (en) | 2010-10-07 |
| CN101688142A (en) | 2010-03-31 |
| WO2009009481A3 (en) | 2009-02-26 |
| RU2010103963A (en) | 2011-08-20 |
| KR20100029119A (en) | 2010-03-15 |
| RU2470067C2 (en) | 2012-12-20 |
| JP2010532763A (en) | 2010-10-14 |
| KR20100029120A (en) | 2010-03-15 |
| RU2010103965A (en) | 2011-08-20 |
| WO2009009293A1 (en) | 2009-01-15 |
| WO2009009481A2 (en) | 2009-01-15 |
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