EP2004780A2 - Lubricant oil additive compositions - Google Patents
Lubricant oil additive compositionsInfo
- Publication number
- EP2004780A2 EP2004780A2 EP07759584A EP07759584A EP2004780A2 EP 2004780 A2 EP2004780 A2 EP 2004780A2 EP 07759584 A EP07759584 A EP 07759584A EP 07759584 A EP07759584 A EP 07759584A EP 2004780 A2 EP2004780 A2 EP 2004780A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hindered phenolic
- boronated
- alkylated diphenylamine
- mono
- composition
- 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- Withdrawn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 91
- 239000000314 lubricant Substances 0.000 title claims abstract description 50
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 32
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 95
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 239000003921 oil Substances 0.000 claims abstract description 74
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 59
- 239000012141 concentrate Substances 0.000 claims abstract description 41
- 239000010687 lubricating oil Substances 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 71
- 229910052750 molybdenum Inorganic materials 0.000 claims description 39
- 239000011733 molybdenum Substances 0.000 claims description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 239000010705 motor oil Substances 0.000 claims description 23
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 3
- 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 claims description 2
- 239000002272 engine oil additive Substances 0.000 claims 8
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000002939 deleterious effect Effects 0.000 abstract description 2
- 235000013824 polyphenols Nutrition 0.000 description 39
- -1 3,3-dimethylbutyl Chemical group 0.000 description 30
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 239000010685 fatty oil Substances 0.000 description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 description 5
- 150000002830 nitrogen compounds Chemical class 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 229940035422 diphenylamine Drugs 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000005078 molybdenum compound Substances 0.000 description 4
- 150000002752 molybdenum compounds Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 2
- JERZAOOJWPHIDG-UHFFFAOYSA-N 2,4-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC=C(O)C(C(C)CC)=C1 JERZAOOJWPHIDG-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000007686 potassium Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000010723 turbine oil Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000010739 combined cycle turbine oil Substances 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- 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 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 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 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOOLFANBWPPEGQ-UHFFFAOYSA-J molybdenum(2+);tetraacetate Chemical compound [Mo+2].[Mo+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O DOOLFANBWPPEGQ-UHFFFAOYSA-J 0.000 description 1
- 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 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000010736 steam turbine oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 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 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
Definitions
- the invention relates to lubricant oil additive compositions and lubricating oil compositions containing the same. More particularly, this invention relates to combinations of hindered phenolic antioxidants, boronated hindered phenolic antioxidants, alkylated diphenylamines and organomolybdenum compounds useful as lubricant oil compositions and lubricating oil additive compositions.
- Hindered phenolic and boronated hindered phenolics are well known in the art, including large molecular phenolics incorporating the moiety, 2,6-di-tert-butylphenol, and the like. See, for example, the following US and foreign patents: US 4,927,553; US 3,356,707; US 3,509,054; US 3,347,793; US 3,014,061; US 3,359,298; US 2,813,830; US 2,462,616; GB 864,840; US 5,698,499; US 5,252,237; US RE 32,295; US 4,547,302; US 3,211,652; and US 2,807,653
- alkylated diphenyl amine as an antioxidant additive in lubricating oil formulations is also well known in the art. See, for example, the following US patents: US 5,620,948; US 5,595,964; US 5,569,644; US 4,857,214; US 4,455,243; and US 5,759,965.
- the present invention generally provides a lubricant oil composition having improved oxidative stability, the composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di- boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound.
- the invention also provides a lubricating oil additive concentrate composition that imparts synergistic oxidative stability to a lubricant oil upon its addition, the concentrate composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound.
- the concentrate compositions of the present invention may also be prepared with a high concentration of hindered phenolic antioxidants without deleterious effects on viscosity or lubricant solubility.
- lubricant oil compositions and lubricating oil additive concentrate compositions comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di- boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound exhibits improved oxidative stability compared to conventional formulations.
- a lubricant oil or lubricating oil additive concentrate composition comprising: (a) 4,4'-methylenebis(2,6-di-tert-butylphenol), (b) 4,4'-methylenebis(2,6-di-tert- butylphenol)-mono-(di-alkyl orthoborate), (c) 4,4'-methylenebis(2,6-di-tert-butylphenol)-di-(di- alkyl orthoborate), (d) an alkylated diphenylamine, and (e) an organomolybdenum compound, is an effective antioxidant combination for use in lubricants.
- a lubricant oil or lubricating oil additive concentrate composition comprising: (a) a hindered phenolic antioxidant, (b) either a single or multiple ortho-borate ester, or combinations thereof, derived from a hindered phenolic antioxidant, wherein the boron is attached to the hindered phenolic oxygen, (c) an alkylated diphenylamine, and (d) an organomolybdenum compound, is an effective antioxidant combination for use in lubricants.
- Hindered phenolics suitable for use in the compositions of the present invention include phenolics incorporating the 2,6-di-tert-butylphenol moiety.
- a suitable hindered phenolic which is commercially sold by Albemarle CorporationTM under the trade name Ethanox® 702, is 4,4'methylenebis(2,6-di-tert-butylphenol), hereinafter referred to as MBDTBP, having the structure of Structure I below: Structure I
- Suitable hindered phenolics include, 2,4-di-tert-butyiphenol, 2,6-di-tert- butylphenol, 6-tert-butyl-ortho-cresoi, 2,6-di-isopropylphenol, 2,4-di-sec-butylphenol, higher molecular weight hindered phenolic antioxidants derived synthetically from 2,4-di-tert- butylphenol, 2,6-di-tert-butylphenol, 6-tert-butyl-ortho-cresol, 2,6-di-isopropylphenol, or 2,4-di- sec-butylphenol, butylated hydroxy toluene (BHT), and the like.
- BHT butylated hydroxy toluene
- the amount of hindered phenolic present in the compositions of the invention ranges from about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine. In additional aspects the amount of hindered phenolic present in the compositions of the invention ranges from about 1 to about 40 weight percent, about 1 to about 30 weight percent, about 1 to about 25 weight percent, about 1 to about 20 weight percent, and about 1 to about 15 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine.
- the mono- and di-boronated hindered phenolics suitable for use in the compositions of the present invention are derived from the hindered phenolics described above by reaction with tri-alkyl orthoborates.
- One such process is disclosed in US 4,927,553.
- suitable mono- and di-boronated hindered phenolics have the structures of Structures II and III below:
- Rj, R 2 , R 3 , and R 4 are independently selected from the group consisting of linear, branched and cyclic Ci to Cg alkyl groups.
- groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, 2-methylbutyl, 3- methylbutyl, 2-methyl ⁇ 2-butyl, 3-methyl-2-butyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, 2- ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2- pentyl, 3-methyl-3-pentyl, 3,3-dimethylbutyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl
- Other mono- and di-boronated hindered phenolics may be derived from reacting the specific hindered phenolics described above, or mixtures of hindered phenolics, with tri-alkyl orthoborates.
- the combined total of mono- and di-boronated hindered phenolics present in the compositions of the invention ranges from about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine.
- the ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic may vary from about 0.01 : 1 to about 1 :0.01.
- the amount of mono-boronated hindered phenolic can be approximately equal to or greater than that of di-boronated hindered phenolic.
- the amount of MBDTBP in conventional lubricant oil additive concentrate compositions has been limited by its solubility to about 10 wt% of the total additive concentrate.
- the present invention provides a method for increasing the concentration of hindered phenolic antioxidant in the lubricant oil additive concentrate composition to be increased to as high as about 50 wt% by including boronated hindered phenolic antioxidants in the lubricant oil additive concentrate composition.
- the alkylated diphenylamines suitable for use in the compositions of the present invention are prepared from diphenylamine by reaction with olefins.
- One particularly useful method of preparing alkylated diphenylamines is described in US Patent Publication US-2006- 0276677-A1 (which related to US 11/442856 filed 30 May 2006, which claims priority to US Provisional Patent Application 60/687,182 filed on June 2, 2005 and to US Provisional Patent Application 60/717322 filed on Sept. 14, 2005), which US Patent Publication is incorporated in its entirety by reference herein to the extent allowed by applicable law.
- Both mono- and di- alkylated diphenylamines may be employed, either alone are in combination, and have the structures shown in Structures IV and V below: Structure IV
- R 1 , R 2 and R 3 are independently selected from the group consisting of linear, branched and cyclic C 4 to C 32 alkyl groups.
- groups include, but are not limited to, alkyl groups derived from linear alpha-olefins, isomerized alpha-olefms polymerized alpha-olefins, low molecular weight oligomers of propylene, and low molecular weight oligomers of isobutylene.
- Specific examples include but are not limited to butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, dipropyl, tripropyl, tetrapropyl, pentapropyl, hexapropyl, heptapropyl, octapropyl, diisobutyl, triisobutyl, tetraisobutyl, pentaisobutyl, hexaisobutyl, and heptaisobutyl.
- the combined total of mono- and di-alkylated diphenylamine present in the compositions of the invention ranges from about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine.
- the ratio of mono- to di-alkylated diphenylamine may vary from about 0,01:1 to about 1 :0.01.
- alkylated diphenylamines examples include nonylated diphenylamines (NDPA), octylated diphenylamines, mixed octylated/styrenated diphenylamines (such as Durad® AX55), and mixed butylated/octylated diphenylamines (such as Vanlube® 961). Further, the nitrogen content of the alkylated diphenylamines can be in the range of about 2.0 to about 6.0 wt. %.
- the alkylated diphenylamines can be a liquid or low melting solid.
- Qrganomolybdemim compounds suitable for use in the present invention include sulfur-free compounds, phosphorus-free compounds, and sulfur-containing compounds.
- the molybdenum content of organomolybdenum compounds may vary from about 1 wt% to about 15 wt%.
- the concentration of the organomolybdenum compound may range from about 1 wt% to about 40 wt% of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
- the amount of organomolybdenum compound used in compositions of the present invention is such that the weight ratio of molybdenum to boron ranges from about 0.01 : 1 to about 10:1.
- the molybdenum content of a lubricant oil can range from between about 50 to about 1000 ppm and the boron content can range between about 50 to about 500 ppm.
- the molybdenum content of a lubricant oil can range from between about 100 to about 400 ppm and the boron content can range between about 100 to about 400 ppm.
- Sulfur- and phosphorus-free organomolybdenum compounds may be prepared by reacting a sulfur and phosphorus-free molybdenum source with an organic compound containing amino and/or alcohol groups.
- sulfur- and phosphorus-free molybdenum sources include molybdenum trioxide, ammonium molybdate, sodium molybdate and potassium molybdate.
- the amino groups may be monoamines, diamines, or polyamines.
- the alcohol groups may be mono-substituted alcohols, diols or bis-alcohols, or polyalcohols.
- the reaction of diamines with fatty oils produces a product containing both amino and alcohol groups that can react with the sulfur- and phosphorus-free molybdenum source.
- Examples of sulfur- and phosphorus-free organomolybdenum compounds suitable for use in the present invention include the following: compounds prepared by reacting certain basic nitrogen compounds with a molybdenum source as defined in U.S. Patent Nos. 4,259,195 and 4,261,843; compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source as defined in U.S. Patent No. 4,164,473; compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source as defined in U.S. Patent No.
- Examples of commercial sulfur- and phosphorus- free oil soluble molybdenum compounds are Sakura-Lube 700 from Asahi Denka, and Molyvan 856B and Molyvan 855 from R. T. Vanderbilt Company, Inc.
- Molybdenum compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source as defined in U. S. Patent 4,889,647 are sometimes illustrated as having one or both of the following structures,
- R is a fatty alkyl chain.
- the exact chemical structure of these materials is not fully known and may in fact be multi-component mixtures of many organomolybdenum compounds.
- Sulfur-containing organomolybdenum compounds may be prepared by a variety of methods. One method involves reacting a sulfur and phosphorus-free molybdenum source with an amino group and one or more sulfur sources. Sulfur sources include carbon disulfide, hydrogen sulfide, sodium sulfide and elemental sulfur. Alternatively, the sulfur-containing molybdenum compound may be prepared by reacting a sulfur containing molybdenum source with an amino group or thiuram group and optionally a second sulfur source. Examples of sulfur- and phosphorus-free molybdenum sources include molybdenum trioxide. ammonium molybdate, sodium molybdate, potassium molybdate and molybdenum halides.
- the amino groups may be monoamines, diamines, or polyamines.
- the reaction of molybdenum trioxide with a secondary amine and carbon disulfide produces molybdenum dithiocarbamates.
- the reaction of (NH4)2Mo 3 Si 3 -n(H 2 O) where n varies between 0 to 2 with a tetralkylthiuram disulfide produces a trinuclear sulfur -containing molybdenum dithiocarbamate.
- sulfur-containing organomolybdenum compounds suitable for use in the present invention include the following: compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide as defined in U.S. Patent Nos. 3,509,051 and 3,356,702; compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source as defined in U.S. Patent No. 4,098,705; compounds prepared by reacting a molybdenum halide with a secondary amine and carbon disulfide as defined in U. S. Patent No.
- Patent 4,995,996 compounds prepared by reacting (NH 4 )2M ⁇ 3 Si 3 -2(H 2 ⁇ ) with an alkali metal dialkyldithiocarbamate or tetralkyl thiuram disulfide as define in U.S. Patent No. 6,232,276; compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide as defined in U.S. Patent No. 6,103,674; and compounds prepared by reacting an alkali metal dialkyldithiocarbamate with 3- chloropropionic acid, followed by molybdenum trioxide, as defined in U.S. Patent No. 6,117,826.
- Examples of commercial sulfur-containing oil soluble molybdenum compounds are Sakura-Lube® 100, Sakura-Lube® 155, Sakura-Lube® 165, and Sakura-Lube® 180 from Asahi Denka Kogyo K.K., Molyvan® A, Molyvan® 807 and Molyvan® 822 from R. T. Vanderbilt Company, and Naugalube® MoIyFM from Crompton Corporation.
- Molybdenum dithiocarbamates are suitable organomolybdenum compounds and have the following structure:
- R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons
- X is independently selected from oxygen or sulfur.
- the lubricating oil may be any basestock or base oil (characterized as Group I, Group II, Group III, Group IV or Group V as defined by the API basestock classification system), or lubricant composed predominately of aromatics, naphthenics, paraff ⁇ nics, poly-alpha-olefins and/or synthetic esters. Further, the lubricant may also contain additional additives so as to make the system acceptable for use in a variety of applications.
- additives include dispersants, detergents, viscosity index improvers, pour point depressants, anti-wear additives, extreme pressure additives, friction modifiers, corrosion inhibitors, rust inhibitors, emulsifiers, demulsifiers, anti-foaming agents, colorants, seal swelling agents, and additional antioxidants.
- the present invention may be useful in passenger car engine oils, heavy duty diesel oils, medium speed diesel oils, railroad oils, marine engine oils, natural gas engine oils, 2-cycle engine oils, steam turbine oils, gas turbine oils, combined cycle turbine oils, R&O oils, industrial gear oils, automotive gear oils, compressor oils, manual transmission fluids, automatic transmission fluids, slideway oils, quench oils, flush oils and hydraulic fluids.
- Suitable applications are in engine oils.
- a suitable application is in low phosphorus engine oils characterized by a phosphorus content of less than 1000 ppm.
- the lubricating oil additive concentrate may or may not contain a diluent oil. If a diluent oil is used, the diluent oil is typically present between 1 and 80 wt. % of the concentrate.
- the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound that are added to fully formulated oils depends upon the end use application.
- the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound added to the oil ranges between about 0.05 and about 1.0 wt. %.
- the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdeum compound added to the oil ranges between about 0.2 and about 3.0 wt.%.
- the total amount of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine may approach 5.0 wt. % or more,
- a passenger car engine oil preblend was prepared in accordance with the present invention by blending the following materials:
- MoDTC Molybdenum dithiocarbamate containing 4 5 wt % molybdenum
- BMBDTBP a sample composed of: 15 6 wt % 4 4-methyleneb ⁇ s(2,6-d ⁇ -tert-butylphenol, 38 6 wt % 4,4'-methyleneb ⁇ s(2,6-d ⁇ -tert-butylphenol)-mono-(d ⁇ -sec-butyI orthoborate), 17.4 wt.% 4,4'- methyleneb ⁇ s(2,6-di-tert-butylphenol)-d ⁇ -(d ⁇ -sec-butyl orthoborate) (values calculated based upon
- HPLC analysis HPLC analysis
- 1 0 wt % of an ashless dispersant 1 0 wt % of an ashless dispersant
- 29 0 wt % of a 500N naphthenic diluent oil The sample has a boron content of 1 23 wt% as determined by ICP.
- HPE S. ⁇ -di-tert-butyM-hydroxyhydrocinnamic acid, C 7 -C 9 branched alkyl esters
- NDPA Nonylated diphenylamine
- G2BO 150N Group Il baseoil
- compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions, methods and/or processes and in the steps or in the sequence of steps of the methods described herein without departing from the concept and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and concept of the invention.
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Abstract
A lubricant oil composition having a synergistic oxidative stability is disclosed, the composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. The invention also provides a lubricating oil additive concentrate composition that imparts synergistic oxidative stability to a lubricant oil upon its addition, the concentrate composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. Further, the concentrate compositions of the present invention may also be prepared with a high concentration of hindered phenolic antioxidants without deleterious effects on viscosity or lubricant solubility.
Description
LUBRICANT OIL ADDITIVE COMPOSITIONS
FIELD OF THE INVENTION
[001] The invention relates to lubricant oil additive compositions and lubricating oil compositions containing the same. More particularly, this invention relates to combinations of hindered phenolic antioxidants, boronated hindered phenolic antioxidants, alkylated diphenylamines and organomolybdenum compounds useful as lubricant oil compositions and lubricating oil additive compositions.
DESCRIPTION OF RELATED ART
[002] Hindered phenolic and boronated hindered phenolics are well known in the art, including large molecular phenolics incorporating the moiety, 2,6-di-tert-butylphenol, and the like. See, for example, the following US and foreign patents: US 4,927,553; US 3,356,707; US 3,509,054; US 3,347,793; US 3,014,061; US 3,359,298; US 2,813,830; US 2,462,616; GB 864,840; US 5,698,499; US 5,252,237; US RE 32,295; US 4,547,302; US 3,211,652; and US 2,807,653
[003] The use of alkylated diphenyl amine as an antioxidant additive in lubricating oil formulations is also well known in the art. See, for example, the following US patents: US 5,620,948; US 5,595,964; US 5,569,644; US 4,857,214; US 4,455,243; and US 5,759,965.
[004] There are many examples in the patent literature showing the use of molybdenum additives as antioxidants, deposit control additives, anti-wear additives and friction modifiers. See, for example, the following US and foreign patents: US 5,840,672; US 5,814,587; US 4,529,526; WO 95/07966; US 5,650,381; US 4,812,246; US 5,458,807; WO 95/07964; US 5,880,073; US 5,658,862; US 5,696,065; WO 95/07963; US 5,665,684; US 4,360,438; US 5,736,491; WO 95/27022; US 5,786,307; US 4,501,678; US 5,688,748; EP 0 447 916 Al; US 5,807,813; US 4,692,256; US 5,605,880; WO 95/07962; US 5,837,657; US 4,832,867; US 4,705,641; EP 0 768 366 Al; US 6,103,674; US 6,010,987; US 6,110,878; EP 1 136 496 Al; US 6,150,309; US 6,232,276; US 6,306,802; EP 1 136 497 Al; US 5,888,945; US 6,187,723; US 6,117,826; US 6,103,674; US 6,063,741; US 6,017,858; US 5,994,277; and US 6,174,842.
SUMMARY OF THE INVENTION
[005] The present invention generally provides a lubricant oil composition having improved oxidative stability, the composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di- boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound. The invention also provides a lubricating oil additive concentrate composition that imparts synergistic oxidative stability to a lubricant oil upon its addition, the concentrate composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound. Further, the concentrate compositions of the present invention may also be prepared with a high concentration of hindered phenolic antioxidants without deleterious effects on viscosity or lubricant solubility.
[006] The synergistic improvement of oxidative stability in lubricant oil compositions and lubricating oil additive concentrate compositions comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di- boronated hindered phenolic antioxidant, and at least one alkylated diphenylamine is disclosed in concurrently filed, commonly owned US Provisional Application 60/758,754 filed on January 13, 2006, and in PCT application number PCT/US2007/060489 that claims priority to US Provisional Application 60/758,754, both of which are hereby incorporated by reference in their entirety to the extent allowed by applicable law. The present invention improves upon the disclosure of US Provisional Application 60/758,754 such that lubricant oil compositions and lubricating oil additive concentrate compositions comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di- boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound exhibits improved oxidative stability compared to conventional formulations.
[007] In one aspect, a lubricant oil or lubricating oil additive concentrate composition comprising: (a) 4,4'-methylenebis(2,6-di-tert-butylphenol), (b) 4,4'-methylenebis(2,6-di-tert- butylphenol)-mono-(di-alkyl orthoborate), (c) 4,4'-methylenebis(2,6-di-tert-butylphenol)-di-(di- alkyl orthoborate), (d) an alkylated diphenylamine, and (e) an organomolybdenum compound, is an effective antioxidant combination for use in lubricants.
[008] In another aspect, a lubricant oil or lubricating oil additive concentrate composition comprising: (a) a hindered phenolic antioxidant, (b) either a single or multiple ortho-borate ester, or combinations thereof, derived from a hindered phenolic antioxidant, wherein the boron is attached to the hindered phenolic oxygen, (c) an alkylated diphenylamine, and (d) an organomolybdenum compound, is an effective antioxidant combination for use in lubricants.
BRIEF DESCRIPTION OF THE FIGURE
[009J Figure 1 shows graphical results from Example A.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Hindered phenolics suitable for use in the compositions of the present invention include phenolics incorporating the 2,6-di-tert-butylphenol moiety. A suitable hindered phenolic, which is commercially sold by Albemarle Corporation™ under the trade name Ethanox® 702, is 4,4'methylenebis(2,6-di-tert-butylphenol), hereinafter referred to as MBDTBP, having the structure of Structure I below: Structure I
[0011] Other suitable hindered phenolics include, 2,4-di-tert-butyiphenol, 2,6-di-tert- butylphenol, 6-tert-butyl-ortho-cresoi, 2,6-di-isopropylphenol, 2,4-di-sec-butylphenol, higher molecular weight hindered phenolic antioxidants derived synthetically from 2,4-di-tert- butylphenol, 2,6-di-tert-butylphenol, 6-tert-butyl-ortho-cresol, 2,6-di-isopropylphenol, or 2,4-di- sec-butylphenol, butylated hydroxy toluene (BHT), and the like.
[0012] The amount of hindered phenolic present in the compositions of the invention ranges from about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine. In additional aspects the amount of
hindered phenolic present in the compositions of the invention ranges from about 1 to about 40 weight percent, about 1 to about 30 weight percent, about 1 to about 25 weight percent, about 1 to about 20 weight percent, and about 1 to about 15 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine.
[0013] The mono- and di-boronated hindered phenolics suitable for use in the compositions of the present invention are derived from the hindered phenolics described above by reaction with tri-alkyl orthoborates. One such process is disclosed in US 4,927,553. In one aspect, suitable mono- and di-boronated hindered phenolics have the structures of Structures II and III below:
wherein Rj, R2, R3, and R4 are independently selected from the group consisting of linear, branched and cyclic Ci to Cg alkyl groups. Examples of such groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, 2-methylbutyl, 3- methylbutyl, 2-methyl~2-butyl, 3-methyl-2-butyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, 2- ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-
pentyl, 3-methyl-3-pentyl, 3,3-dimethylbutyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2- methyl-2-hexyl, 2,2-dimethyl-3-pentyl, 2-heptyl, 3-heptyl, 2-methyl-3-hexyl, 3-ethyl-3-pentyl, 2,3-dimethyl-3~pentyl, 2,4-dimethyl-3 -pentyl, 5-methyl-2-hexyl, 4,4-dimethyl-2-pentyl, 5- methylhexyl, n-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, 3-octyl, 2,44- trimethylpentyl, 4-methyl-3-heptyl and 6-methyl-2-heptyl.
[0014] Other mono- and di-boronated hindered phenolics may be derived from reacting the specific hindered phenolics described above, or mixtures of hindered phenolics, with tri-alkyl orthoborates.
[0015] The combined total of mono- and di-boronated hindered phenolics present in the compositions of the invention ranges from about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine. The ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic may vary from about 0.01 : 1 to about 1 :0.01. The amount of mono-boronated hindered phenolic can be approximately equal to or greater than that of di-boronated hindered phenolic.
[0016] The amount of MBDTBP in conventional lubricant oil additive concentrate compositions has been limited by its solubility to about 10 wt% of the total additive concentrate. However, the present invention provides a method for increasing the concentration of hindered phenolic antioxidant in the lubricant oil additive concentrate composition to be increased to as high as about 50 wt% by including boronated hindered phenolic antioxidants in the lubricant oil additive concentrate composition.
[0017] The alkylated diphenylamines suitable for use in the compositions of the present invention are prepared from diphenylamine by reaction with olefins. One particularly useful method of preparing alkylated diphenylamines is described in US Patent Publication US-2006- 0276677-A1 (which related to US 11/442856 filed 30 May 2006, which claims priority to US Provisional Patent Application 60/687,182 filed on June 2, 2005 and to US Provisional Patent Application 60/717322 filed on Sept. 14, 2005), which US Patent Publication is incorporated in its entirety by reference herein to the extent allowed by applicable law. Both mono- and di- alkylated diphenylamines may be employed, either alone are in combination, and have the structures shown in Structures IV and V below:
Structure IV
Structure V
wherein R1, R2 and R3 are independently selected from the group consisting of linear, branched and cyclic C4 to C32 alkyl groups. Examples of such groups include, but are not limited to, alkyl groups derived from linear alpha-olefins, isomerized alpha-olefms polymerized alpha-olefins, low molecular weight oligomers of propylene, and low molecular weight oligomers of isobutylene. Specific examples include but are not limited to butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, dipropyl, tripropyl, tetrapropyl, pentapropyl, hexapropyl, heptapropyl, octapropyl, diisobutyl, triisobutyl, tetraisobutyl, pentaisobutyl, hexaisobutyl, and heptaisobutyl.
[0018] The combined total of mono- and di-alkylated diphenylamine present in the compositions of the invention ranges from about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine. The ratio of mono- to di-alkylated diphenylamine may vary from about 0,01:1 to about 1 :0.01.
[0019] Examples of suitable alkylated diphenylamines are nonylated diphenylamines (NDPA), octylated diphenylamines, mixed octylated/styrenated diphenylamines (such as Durad® AX55), and mixed butylated/octylated diphenylamines (such as Vanlube® 961). Further, the nitrogen content of the alkylated diphenylamines can be in the range of about 2.0 to about 6.0 wt. %. Lower levels of nitrogen dilute the effectiveness of the alkylated diphenylamines while higher levels of nitrogen may adversely impact compatibility of the alkylated diphenylamines in the lubricant or the lubricant's volatility. The alkylated diphenylamines can be a liquid or low melting solid.
[0020] Qrganomolybdemim compounds suitable for use in the present invention include sulfur-free compounds, phosphorus-free compounds, and sulfur-containing compounds. The
molybdenum content of organomolybdenum compounds may vary from about 1 wt% to about 15 wt%. The concentration of the organomolybdenum compound may range from about 1 wt% to about 40 wt% of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
[0021] The amount of organomolybdenum compound used in compositions of the present invention is such that the weight ratio of molybdenum to boron ranges from about 0.01 : 1 to about 10:1. The molybdenum content of a lubricant oil can range from between about 50 to about 1000 ppm and the boron content can range between about 50 to about 500 ppm. The molybdenum content of a lubricant oil can range from between about 100 to about 400 ppm and the boron content can range between about 100 to about 400 ppm.
[0022] Sulfur- and phosphorus-free organomolybdenum compounds may be prepared by reacting a sulfur and phosphorus-free molybdenum source with an organic compound containing amino and/or alcohol groups. Examples of sulfur- and phosphorus-free molybdenum sources include molybdenum trioxide, ammonium molybdate, sodium molybdate and potassium molybdate. The amino groups may be monoamines, diamines, or polyamines. The alcohol groups may be mono-substituted alcohols, diols or bis-alcohols, or polyalcohols. As an example, the reaction of diamines with fatty oils produces a product containing both amino and alcohol groups that can react with the sulfur- and phosphorus-free molybdenum source.
[0023] Examples of sulfur- and phosphorus-free organomolybdenum compounds suitable for use in the present invention include the following: compounds prepared by reacting certain basic nitrogen compounds with a molybdenum source as defined in U.S. Patent Nos. 4,259,195 and 4,261,843; compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source as defined in U.S. Patent No. 4,164,473; compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source as defined in U.S. Patent No. 4,266,945; compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source as defined in U.S. Patent No. 4,889,647; compounds prepared by reacting a fatty oil or acid with 2-(2-aminoethyl)aminoethanol, and a molybdenum source as defined in U.S. Patent No. 5,137,647; compounds prepared by reacting a secondary amine with a molybdenum source as defined in U.S. Patent No. 4,692,256; compounds prepared by reacting a diol, diamino, or amino-alcohol compound with a molybdenum source as defined in U.S. Patent No. 5,412,130; compounds prepared by reacting a fatty oil, mono-alkylated alkylene diamine, and a molybdenum source as defined in European Patent Application EP 1 136 496 Al ; and compounds prepared by reacting a fatty acid, mono-
alkylated alkylene diamine, glycerides, and a molybdenum source as defined in European Patent Application EP 1 136 497 Al.
[0024] Examples of commercial sulfur- and phosphorus- free oil soluble molybdenum compounds are Sakura-Lube 700 from Asahi Denka, and Molyvan 856B and Molyvan 855 from R. T. Vanderbilt Company, Inc.
[0025] Molybdenum compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source as defined in U. S. Patent 4,889,647 are sometimes illustrated as having one or both of the following structures,
wherein R is a fatty alkyl chain. The exact chemical structure of these materials is not fully known and may in fact be multi-component mixtures of many organomolybdenum compounds.
[0026] Sulfur-containing organomolybdenum compounds may be prepared by a variety of methods. One method involves reacting a sulfur and phosphorus-free molybdenum source with an amino group and one or more sulfur sources. Sulfur sources include carbon disulfide, hydrogen sulfide, sodium sulfide and elemental sulfur. Alternatively, the sulfur-containing molybdenum compound may be prepared by reacting a sulfur containing molybdenum source with an amino group or thiuram group and optionally a second sulfur source. Examples of sulfur- and phosphorus-free molybdenum sources include molybdenum trioxide. ammonium molybdate, sodium molybdate, potassium molybdate and molybdenum halides. The amino groups may be monoamines, diamines, or polyamines. As an example, the reaction of molybdenum trioxide with a secondary amine and carbon disulfide produces molybdenum dithiocarbamates. Alternatively, the reaction of (NH4)2Mo3Si3-n(H2O) where n varies between 0 to 2 with a tetralkylthiuram disulfide produces a trinuclear sulfur -containing molybdenum dithiocarbamate.
[0027] Examples of sulfur-containing organomolybdenum compounds suitable for use in the present invention include the following: compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide as defined in U.S. Patent Nos. 3,509,051 and 3,356,702; compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source as defined in U.S. Patent No. 4,098,705; compounds prepared by reacting a molybdenum halide with a secondary amine and carbon
disulfide as defined in U. S. Patent No. 4,178,258; compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source as defined in U.S. Patent Nos. 4,263,152, 4,265,773, 4,272,387, 4,285,822, 4,369,119, and 4,395,343: compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound as defined in U.S. Patent No. 4,283,295; compounds prepared by reacting an olefin, sulfur, an amine and a molybdenum source as defined in U.S. Patent No. 4,362,633; compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source as defined in U.S. Patent No. 4,402,840; compounds prepared by reacting a phenolic compound, an amine and a molybdenum source with a sulfur source as defined in U.S. Patent No, 4,466,901 ; compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source as defined in U.S. Patent No. 4,765,918; compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides as defined in U.S. Patent No. 4,966,719; compounds prepared by reacting a tetralkylthiuram disulfide with molybdenum hexacarbonyl as defined in U. S. Patent No. 4,978,464; compounds prepared by reacting an alkyl dixanthogen with molybdenum hexacarbonyl as defined in U.S. Patent No. 4,990,271; compounds prepared by reacting alkali metal alkylxanthate salts with dimolybdenum tetraacetate as defined in U.S. No. Patent 4,995,996; compounds prepared by reacting (NH4)2Mθ3Si3-2(H2θ) with an alkali metal dialkyldithiocarbamate or tetralkyl thiuram disulfide as define in U.S. Patent No. 6,232,276; compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide as defined in U.S. Patent No. 6,103,674; and compounds prepared by reacting an alkali metal dialkyldithiocarbamate with 3- chloropropionic acid, followed by molybdenum trioxide, as defined in U.S. Patent No. 6,117,826.
[0028] Examples of commercial sulfur-containing oil soluble molybdenum compounds are Sakura-Lube® 100, Sakura-Lube® 155, Sakura-Lube® 165, and Sakura-Lube® 180 from Asahi Denka Kogyo K.K., Molyvan® A, Molyvan® 807 and Molyvan® 822 from R. T. Vanderbilt Company, and Naugalube® MoIyFM from Crompton Corporation.
[0029] Molybdenum dithiocarbamates are suitable organomolybdenum compounds and have the following structure:
wherein R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons, and X is independently selected from oxygen or sulfur.
[0030] The lubricating oil may be any basestock or base oil (characterized as Group I, Group II, Group III, Group IV or Group V as defined by the API basestock classification system), or lubricant composed predominately of aromatics, naphthenics, paraffϊnics, poly-alpha-olefins and/or synthetic esters. Further, the lubricant may also contain additional additives so as to make the system acceptable for use in a variety of applications. These additives include dispersants, detergents, viscosity index improvers, pour point depressants, anti-wear additives, extreme pressure additives, friction modifiers, corrosion inhibitors, rust inhibitors, emulsifiers, demulsifiers, anti-foaming agents, colorants, seal swelling agents, and additional antioxidants.
[0031] The present invention may be useful in passenger car engine oils, heavy duty diesel oils, medium speed diesel oils, railroad oils, marine engine oils, natural gas engine oils, 2-cycle engine oils, steam turbine oils, gas turbine oils, combined cycle turbine oils, R&O oils, industrial gear oils, automotive gear oils, compressor oils, manual transmission fluids, automatic transmission fluids, slideway oils, quench oils, flush oils and hydraulic fluids. Suitable applications are in engine oils. A suitable application is in low phosphorus engine oils characterized by a phosphorus content of less than 1000 ppm.
[0032] The lubricating oil additive concentrate may or may not contain a diluent oil. If a diluent oil is used, the diluent oil is typically present between 1 and 80 wt. % of the concentrate.
[0033] Typically, the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound that are added to fully formulated oils depends upon the end use application. For example, in a turbine oil the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound added to the oil ranges between about 0.05 and about 1.0 wt. %. In contrast, in an engine oil the total amount of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdeum compound added to the oil ranges between about 0.2 and about 3.0 wt.%. In ultra-low phosphorus engine oils the total amount of hindered phenolic, boronated hindered phenolic, and alkylated diphenylamine may approach 5.0 wt. % or more,
[0034] An example of a lubricating oil additive concentrate in accordance with the present invention is as follows:
(a) 4,4-methylenebis(2,6-di-tert-butylphenol) @ 10 wt. %;
(b) 4,4'-methylenebis(2,6-di-tert-butylphenol) mono-(di-sec-butyl orthoborate) and 4,4'- methylenebis(2,6-di-tert-butylphenol) di-(di-sec-butyl orthoborate) @ 40 wt. %;
(c) dinonyldiphenylamine and monononyldiphenylamine @ 10 wt. %;
(d) a molybdenum dithiocarbamate containing 4.5 wt.% molybdenum @ 20 wt.%; and
(e) paraffinic diluent oil @ 20 wt. %.
[0035] An example of a low phosphorus engine oil in accordance with the present invention is as follows:
(a) 4,4-methylenebis(2,6-di-tert-butylphenol) @ 0.5 wt. %;
(b) 4,4'-methylenebis(2,6-di-tert-butylphenol) mono-(di-sec-butyl orthoborate) and 4,4'- methylenebis(2,6-di-tert-butylphenol) di-(di-sec-butyl orthoborate) @ 1.0 wt. %;
(c) dinonyldiphenylamine and monononyldiphenylamine @ 0.75 wt. %;
(d) a molybdenum dithiocarbamate containing 4.5 wt.% molybdenum @ 0.2 wt.%
(e) a dispersant concentrate @ 4.8 wt. %;
(f) an overbased calcium detergent concentrate @ 1.8 wt. %;
(g) a neutral calcium detergent concentrate @ 0.5 wt. %; (h) zinc dialkyldithiophosphate @ 0.6 weight %;
(i) a pour point depressant at 0.1 wt. %; (j) a viscosity index improver concentrate @ 8.0 wt. %; (k) an organic friction modifier @ 0.5 wt. %; and (1) paraffinic lubricating oil @ 81.25 wt. % Example A: Oil thickening and Oxidation at Elevated Temperatures
[0036] A passenger car engine oil preblend was prepared in accordance with the present invention by blending the following materials:
(a) 5.000 wt. % of an ashless dispersant;
(b) 1.875 wt. % of an overbased detergent containing calcium;
(c) 0.521 wt. % of a neutral detergent containing calcium;
(d) 0.625 wt. % of a secondary zinc dialkyldithiophosphate; and
(e) 91.979 wt. % of a 150N Group II baseoil.
To this engine oil preblend was added the components indicated in Table 1.
Table 1. Components of Examples A.1-A.6.
MoDTC = Molybdenum dithiocarbamate containing 4 5 wt % molybdenum
BMBDTBP = a sample composed of: 15 6 wt % 4 4-methylenebιs(2,6-dι-tert-butylphenol, 38 6 wt % 4,4'-methylenebιs(2,6-dι-tert-butylphenol)-mono-(dι-sec-butyI orthoborate), 17.4 wt.% 4,4'- methylenebιs(2,6-di-tert-butylphenol)-dι-(dι-sec-butyl orthoborate) (values calculated based upon
HPLC analysis), 1 0 wt % of an ashless dispersant, and 29 0 wt % of a 500N naphthenic diluent oil. The sample has a boron content of 1 23 wt% as determined by ICP.
HPE = S.δ-di-tert-butyM-hydroxyhydrocinnamic acid, C7-C9branched alkyl esters
NDPA = Nonylated diphenylamine
G2BO = 150N Group Il baseoil
[0037] The oxidative stability of these finished engine oils was evaluated in a bulk oil oxidation test. Each oil (300 niL) was treated with an iron naphthenate oxidation catalyst to deliver 110 ppm of iron to the finished oil. The oils were heated in a block heater at 1500C, while 10 liters/hour of dry oxygen was bubbled through the oil. Samples of the oxidized oils were removed at 24, 48, 72, 96, 120, 144, 168 and 192 hours. Kinematic viscosities of each sample were determined at 400C. The percent viscosity increase of the oxidized oil versus the fresh oil was calculated. The percent viscosity increase results are shown in Table 2.
Table 2. Percent viscosity increase of finished oils A.1-A.6 in bulk oil oxidation test.
[0038] A higher percent viscosity increase is a measure of increased oxidation and degradation of the lubricant. These results clearly show that the inventive antioxidant combination in Examples A.3 to A.6 provide superior oxidation protection compared to the other Examples (A.I -A.2). Antioxidant systems that do not contain the combination of 4,4'- methylenebis(2,6-di-tert~butylphenol), boronated 4,4'-methylenebis(2,6-di-tert-butylphenol), nonylated diphenylamine and organomolybdenum compound show poor oxidation control while systems containing BMBDTBP, NDPA and MoDTC show superior oxidative control. These results are shown graphically in Figure 1.
Example B - Pressurized Differential Scanning Calorimetry (PDSC)
[0039] The oxidative stability of the finished engine oils prepared in Example A was evaluated using pressurized differential scanning calorimetry following the ASTM standard test method D 6186 and using the following operation conditions: isothermal temperature = 18O0C, oxygen gas @ 500 psig with a flow rate of 100 mL/min5 approximately 3 mg sample size, open aluminum pans. Each oil was treated with an iron naphthenate oxidation catalyst to deliver 55 ppm of iron to the finished oil. Oxidation induction times (OIT) were determined according to the ASTM method. Each oil was tested in duplicate and the results averaged. The OIT results are shown in Table 3.
Table 3. Oxidation Induction Times in minutes for finished oils A.1-A.6 tested using PDSC.
[0040] A longer induction time is a measure of increased oxidation stability of the lubricant. These results clearly show that the inventive antioxidant combination in Examples A.4 to A.6 provide superior oxidation protection compared to the non-inventive Examples (A.I -A.2). Antioxidant systems that do not contain the combination of 4,4'-methylenebis(2,6-di-tert- butylphenol), boronated 4,4'-methylenebis(2,6-di-tert-butylphenol), nonylated diphenylamine and molybdenum show poor oxidation control while systems containing BMDTBP, NDPA and MoDTC show superior oxidative control. Also, considerably less, i.e. 25 % less, antioxidant is used in inventive oil A.3 versus non-inventive oil A.2 in order to deliver the same performance level in the PDSC (1 12.12 minutes and 110.77 minutes statistically equivalent).
[0041] While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions, methods and/or processes and in the steps or in the sequence of steps of the methods described herein without departing from the concept and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and concept of the invention.
Claims
1. A lubricant oil composition comprising at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound.
2. The lubricant oil composition of claim 1, wherein the at least one boronated hindered phenolic antioxidant is derived from the at least one hindered phenolic antioxidant.
3. The lubricant oil composition of claim 2, wherein the at least one boronated hindered phenolic antioxidant comprises mono- and di-boronated hindered phenolic antioxidants.
4. The lubricant oil composition of claim 3, wherein the hindered phenolic antioxidant is 4,4'-methylenebis(2,6-di-tert-butylphenol).
5. The lubricant oil composition of claim 4, wherein the mono-boronated hindered phenolic antioxidant has the structure
and the di-boronated hindered phenolic antioxidant has the structure wherein Rj, R2, R3, and R4 are independently selected from the group consisting of linear C) to Cs alkyl groups, branched Ci to C§ alkyl groups and cyclic C3 to Cg alkyl groups.
6. The lubricant oil composition of claim 5, wherein the at least one alkylated diphenylamine comprises mono- and di-alkylated diphenylamine.
7. The lubricant oil composition of claim 6, wherein the mono-alkylated diphenylamine has the structure
and the di-alkylated diphenylamine has the structure
wherein R1, R2 and R3 are independently selected from the group consisting of linear, branched and cyclic C4 to C 32 alkyl groups.
8. The lubricant oil composition of claim 7, wherein the mono- and di-alkylated diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, mixed octylated/styrenated diphenylamines, and mixed butylated/octylated diphenylamines.
9. The lubricant oil composition of claim 3, wherein the organomolybdenum compound is selected from the group consisting of sulfur- free organomolybdenum compounds, phosphorus- free organomolybdenum compounds, and sulfur-containing organomolybdenum compounds.
10. The lubricant oil composition of claim 9, wherein the organomolybdenum compound is a molybdenum dithiocarbamate having the structure
wherein R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons, and X is independently selected from oxygen or sulfur.
11. The lubricant oil composition of claim 10, wherein the concentration of the organomolybdenum compound ranges from about 1 wt% to about 40 wt% of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
12. The lubricant oil composition of claim 11, wherein the weight ratio of molybdenum to boron ranges from about 0.01:1 to about 10:1.
13. The lubricant oil composition of claim 12, wherein the molybdenum content ranges from between about 50 ppm to about 1000 ppm and the boron content ranges between about 50 ppm to about 500 ppm.
14. The lubricant oil composition of claim 13, wherein the molybdenum content ranges from between about 100 ppm to about 400 ppm and the boron content ranges between about 100 ppm to about 400 ppm.
15. The lubricant oil composition of claim 4, wherein the concentration of 4,4'- methylenebis(2,6-di-tert-butylphenol) is between about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
16. The lubricant oil composition of claim 15, wherein the concentration of mono- and di- boronated hindered phenolic is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
17. The lubricant oil composition of claim 16, wherein the ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic is between about 1:1 to about 1:0.01.
18. The lubricant oil composition of claim 17, wherein the concentration of alkylated diphenylamine is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound.
19. A lubricating oil additive concentrate composition comprising at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound.
20. The lubricating oil additive concentrate composition of claim 19, wherein the at least one boronated hindered phenolic antioxidant is derived from the at least one hindered phenolic antioxidant.
21. The lubricating oil additive concentrate composition of claim 20, wherein the at least one boronated hindered phenolic antioxidant comprises mono- and di-boronated hindered phenolic antioxidants.
22. The lubricating oil additive concentrate composition of claim 21, wherein the hindered phenolic antioxidant is 4,4'-methylenebis(2,6-di-tert-butylphenol).
23. The lubricating oil additive concentrate composition of claim 22, wherein the mono- boronated hindered phenolic antioxidant has the structure
and the di-boronated hindered phenolic antioxidant has the structure
wherein R1, R2, R3, and R4 are independently selected from the group consisting of linear C1 to Cz alkyl groups, branched Ci to Cg alkyl groups and cyclic C3 to C8 alkyl groups.
24. The lubricating oil additive concentrate composition of claim 23, wherein the at least one alkylated alkylated diphenylamine comprises mono- and di-alkylated diphenylamine.
25. The lubricating oil additive concentrate composition of claim 24, wherein the mono- alkylated diphenylamine has the structure
and the di-alkylated diphenylamine has the structure
wherein R1, R2 and R3 are independently selected from the group consisting of linear, branched and cyclic C4 to C32 alkyl groups.
26. The lubricating oil additive concentrate composition of claim 25, wherein the mono- and di-alkylated diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, mixed octylated/styrenated diphenylamines, and mixed butylated/octylated diphenylamines.
27. The lubricant oil composition of claim 21, wherein the organomolybdenum compound is selected from the group consisting of sulfur-free organomolybdenum compounds, phosphorus- free organomolybdenum compounds, and sulfur-containing organomolybdenum compounds.
28. The lubricant oil composition of claim 27, wherein the organomolybdenum compound is a molybdenum dithiocarbamate having the structure
wherein R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons, and X is independently selected from oxygen or sulfur.
29. The lubricant oil composition of claim 28, wherein the concentration of the organomolybdenum compound ranges from about 1 wt% to about 40 wt% of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
30. The lubricating oil additive concentrate composition of claim 22. wherein the concentration of 4,4'-methylenebis(2,6-di-tert-butyiphenol) is between about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
31. The lubricating oil additive concentrate composition of claim 30, wherein the concentration of mono- and di-boronated hindered phenolic is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenyiamine and organomolybdenum compound.
32. The lubricating oil additive concentrate composition of claim 31, wherein the ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic is between about 1 : 1 to about 1 :0.01.
33. The lubricating oil additive concentrate composition of claim 32, wherein the concentration of alkylated diphenylamine is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
34. The lubricating oil additive concentrate composition of claim 33, further comprising a diluent oil.
35. The lubricating oil additive concentrate composition of claim 34, wherein the concentration of the diluent oil is between about 1 to about 80 wt%.
36. An engine oil composition comprising at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound.
37. The engine oil composition of claim 36, wherein the hindered phenolic antioxidant is
4,4'-methylenebis(2,6-di-tert-butylphenol).
38. The engine oil composition of claim 37, wherein the at least one boronated hindered phenolic antioxidant comprises a mono-boronated hindered phenolic antioxidant having the structure
and a di-boronated hindered phenolic antioxidant having the structure wherein R1, R2, R3, and R4 are independently selected from the group consisting of linear Ci to Cg alkyl groups, branched Ci to Cs alkyl groups and cyclic C3 to Cs alkyl groups.
39. The engine oil composition of claim 38, wherein the at least one alkylated diphenylamine comprises a mono-alkylated diphenylamine having the structure
and a di-alkylated diphenylamine having the structure
wherein Ri, R2 and R3 are independently selected from the group consisting of linear, branched and cyclic C4 to C32 alkyl groups.
40. The engine oil composition of claim 39, wherein the mono- and di-alkylated diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, mixed octylated/styrenated diphenylamines, and mixed butylated/octylated diphenylamines.
41. The engine oil composition of claim 40, wherein the organomolybdenum compound is a molybdenum dithiocarbamate having the structure
wherein R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons, and X is independently selected from oxygen or sulfur.
42. The engine oil composition of claim 41 , wherein the concentration of 4,4'- methylenebis(2,6-di-tert-butylphenol) is between about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, the concentration of mono- and di-boronated hindered phenolic is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, the ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic is between about 1 :1 to about 1 :0.01, the concentration of alkylated diphenylamine is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, and the concentration of organomolybdenum compound is between about 1 to about 40 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
43. The engine oil composition of claim 42, wherein the engine oil is used to lubricate an engine selected from the group consisting of a gasoline engine, a heavy duty diesel engine, a natural gas engine, a marine engine and a railroad engine.
44. An engine oil additive concentrate composition comprising at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound.
45. The engine oil additive concentrate composition of claim 44, wherein the hindered phenolic antioxidant is 4,4'-methylenebis(2,6-di-tert-butylphenol).
46. The engine oil additive concentrate composition of claim 45, wherein the at least one boronated hindered phenolic antioxidant comprises a mono-boronated hindered phenolic antioxidant having the structure
and a di-boronated hindered phenolic antioxidant having the structure
wherein R1, R2, R3, and R4 are independently selected from the group consisting of linear C1 to Cg alkyl groups, branched Ci to Cs alkyl groups and cyclic C3 to Cs alkyl groups.
47. The engine oil additive concentrate composition of claim 46, wherein the at least one alkylated diphenylamine comprises a mono-alkylated diphenylamine having the structure and a di-alkylated diphenylamine having the structure
wherein R1, R2 and R3 are independently selected from the group consisting of linear, branched and cyclic C4 to C32 alkyl groups.
48. The engine oil additive concentrate composition of claim 47, wherein the mono- and di- alkylated diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, mixed octylated/styrenated diphenylamines, and mixed butylated/octylated diphenylamines.
49. The engine oil additive concentrate composition of claim 48, wherein the organomolybdenum compound is a molybdenum dithiocarbamate having the structure
wherein R is independently selected from hydrogen or an alkyl group containing 4 to 18 carbons, and X is independently selected from oxygen or sulfur.
50. The engine oil additive concentrate composition of claim 49, wherein the concentration of 4,4'-methylenebis(2,6-di-tert-butylphenol) is between about 1 to about 50 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, the concentration of mono- and di- boronated hindered phenolic is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, the ratio of mono-boronated hindered phenolic to di-boronated hindered phenolic is between about 1 :1 to about 1 :0.01, the concentration of alkylated diphenylamine is between about 10 to about 80 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound, and the concentration of organomolybdenum compound is between about 1 to about 40 weight percent of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum compound.
51. The engine oil additive concentrate composition of claim 50, wherein the engine oil is used to lubricate an engine selected from the group consisting of a gasoline engine, a heavy duty diesel engine, a natural gas engine, a marine engine and a railroad engine.
52. A method of increasing the concentration of at least one hindered phenolic antioxidant in a lubricant oil additive concentrate composition, the method comprising the step of adding at least one boronated hindered phenolic antioxidant to the lubricant oil additive concentrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78733406P | 2006-03-29 | 2006-03-29 | |
| PCT/US2007/065371 WO2007115042A2 (en) | 2006-03-29 | 2007-03-28 | Lubricant oil additive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2004780A2 true EP2004780A2 (en) | 2008-12-24 |
Family
ID=37110316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07759584A Withdrawn EP2004780A2 (en) | 2006-03-29 | 2007-03-28 | Lubricant oil additive compositions |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20100286004A1 (en) |
| EP (1) | EP2004780A2 (en) |
| JP (1) | JP2009531533A (en) |
| KR (1) | KR20080103588A (en) |
| CN (1) | CN101415805A (en) |
| AU (1) | AU2007233234A1 (en) |
| BR (1) | BRPI0710256A2 (en) |
| CA (1) | CA2647574A1 (en) |
| EA (1) | EA200870386A1 (en) |
| TW (1) | TW200801174A (en) |
| WO (1) | WO2007115042A2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897552B2 (en) | 2007-11-30 | 2011-03-01 | Afton Chemical Corporation | Additives and lubricant formulations for improved antioxidant properties |
| US8748357B2 (en) | 2008-07-15 | 2014-06-10 | Exxonmobil Research And Engineering Company | Method for stabilizing diesel engine lubricating oil against degradation by biodiesel fuel |
| US20100152074A1 (en) | 2008-12-17 | 2010-06-17 | Chevron Oronite Company Llc | Lubricating oil compositions |
| US20100152073A1 (en) * | 2008-12-17 | 2010-06-17 | Chevron Oronite Company Llc | Lubricating oil compositions |
| US20100152072A1 (en) | 2008-12-17 | 2010-06-17 | Chevron Oronite Company Llc | Lubricating oil compositions |
| CN102812111B (en) * | 2010-03-25 | 2014-06-04 | 范德比尔特化学品有限责任公司 | Ultra low phosphorus lubricant compositions |
| US8334242B2 (en) * | 2010-10-12 | 2012-12-18 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid |
| WO2012173774A1 (en) * | 2011-06-17 | 2012-12-20 | Lubrigreen Biosynthetics, Llc | Estolide compositions exhibiting high oxidative stability |
| KR101974660B1 (en) * | 2013-04-26 | 2019-05-02 | 에스케이이노베이션 주식회사 | Excellent Oxidation Stable and Color Stable Lubricant Composition |
| CN104345085A (en) * | 2013-08-01 | 2015-02-11 | 中国石油化工股份有限公司 | An electrolytic solution and uses thereof |
| FR3032710B1 (en) * | 2015-02-17 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | TIRE WITH BEARING BAND COMPRISING A PHENOLIC COMPOUND |
| GB2579405B (en) | 2018-11-30 | 2022-09-14 | Si Group Switzerland Chaa Gmbh | Antioxidant compositions |
| JP2022526904A (en) * | 2019-03-22 | 2022-05-27 | シェブロン・オロナイト・カンパニー・エルエルシー | Antioxidants with high monoalkylated diphenylamine content |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL283613A (en) * | 1961-09-25 | |||
| DE3361381D1 (en) * | 1982-03-22 | 1986-01-16 | Ethyl Corp | Boron-containing esters, their preparation and use as antioxidants |
| US4927553A (en) * | 1983-05-06 | 1990-05-22 | Ethyl Corporation | Haze-free boronated antioxidant |
| GB9318928D0 (en) * | 1993-09-13 | 1993-10-27 | Exxon Research Engineering Co | Lubricant composition containing combination of antiwear and antioxidant additives |
| EP0796310B1 (en) * | 1994-12-09 | 2001-08-01 | Infineum USA L.P. | Synergistic antioxidant systems |
| US6569818B2 (en) * | 2000-06-02 | 2003-05-27 | Chevron Oronite Company, Llc | Lubricating oil composition |
| KR20020001594A (en) * | 2000-06-26 | 2002-01-09 | 가마이 고로 | Light pipe, plane light source unit and reflection type liquid-crystal display device |
| US6777378B2 (en) * | 2002-02-15 | 2004-08-17 | The Lubrizol Corporation | Molybdenum, sulfur and boron containing lubricating oil composition |
-
2007
- 2007-03-23 TW TW096110093A patent/TW200801174A/en unknown
- 2007-03-28 EA EA200870386A patent/EA200870386A1/en unknown
- 2007-03-28 JP JP2009503250A patent/JP2009531533A/en not_active Withdrawn
- 2007-03-28 WO PCT/US2007/065371 patent/WO2007115042A2/en active Application Filing
- 2007-03-28 BR BRPI0710256-9A patent/BRPI0710256A2/en not_active IP Right Cessation
- 2007-03-28 EP EP07759584A patent/EP2004780A2/en not_active Withdrawn
- 2007-03-28 US US12/294,441 patent/US20100286004A1/en not_active Abandoned
- 2007-03-28 CN CNA2007800116504A patent/CN101415805A/en active Pending
- 2007-03-28 KR KR1020087023865A patent/KR20080103588A/en not_active Withdrawn
- 2007-03-28 AU AU2007233234A patent/AU2007233234A1/en not_active Abandoned
- 2007-03-28 CA CA002647574A patent/CA2647574A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2007115042A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080103588A (en) | 2008-11-27 |
| EA200870386A1 (en) | 2009-04-28 |
| WO2007115042A3 (en) | 2008-01-24 |
| AU2007233234A1 (en) | 2007-10-11 |
| CN101415805A (en) | 2009-04-22 |
| US20100286004A1 (en) | 2010-11-11 |
| BRPI0710256A2 (en) | 2011-08-09 |
| CA2647574A1 (en) | 2007-10-11 |
| WO2007115042A2 (en) | 2007-10-11 |
| TW200801174A (en) | 2008-01-01 |
| JP2009531533A (en) | 2009-09-03 |
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