US20060052255A1 - Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof - Google Patents
Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof Download PDFInfo
- Publication number
- US20060052255A1 US20060052255A1 US10/935,395 US93539504A US2006052255A1 US 20060052255 A1 US20060052255 A1 US 20060052255A1 US 93539504 A US93539504 A US 93539504A US 2006052255 A1 US2006052255 A1 US 2006052255A1
- Authority
- US
- United States
- Prior art keywords
- lubricant composition
- viscosity
- internal combustion
- aromatic hydrocarbon
- combustion engine
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 239000000314 lubricant Substances 0.000 title claims abstract description 76
- 229920000359 diblock copolymer Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000012141 concentrate Substances 0.000 title claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 title description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract description 30
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 28
- 230000001050 lubricating effect Effects 0.000 claims abstract description 25
- 150000001993 dienes Chemical class 0.000 claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 30
- 239000002270 dispersing agent Substances 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 17
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 150000003440 styrenes Chemical class 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000005266 diarylamine group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000004071 soot Substances 0.000 abstract description 22
- 235000019198 oils Nutrition 0.000 description 28
- 239000000178 monomer Substances 0.000 description 19
- -1 shale Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 239000010705 motor oil Substances 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical group C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical class COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-BQYQJAHWSA-N [(e)-2-methoxyethenyl]benzene Chemical class CO\C=C\C1=CC=CC=C1 CTHJQRHPNQEPAB-BQYQJAHWSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000011952 anionic catalyst Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 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 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- 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
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
- C10N2030/041—Soot induced viscosity control
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
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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
Definitions
- the present invention involves lubricant and concentrate compositions and methods thereof that comprise a diblock copolymer.
- the compositions and methods of this invention are especially useful for improving viscosity performance in an internal combustion engine.
- Compression-ignited internal combustion engines also termed diesel engines, of the heavy duty type can use exhaust gas recirculation (EGR) in efforts to reduce engine exhaust emissions of substances, such as nitrogen oxides, that are being regulated for health and environmental concerns.
- EGR exhaust gas recirculation
- the oil or lubricant composition exhibit minimal viscosity increase such as for example less than 12 mm 2 /sec (cSt) at a soot loading of 6%.
- a lubricant composition that has less change in its viscosity with a change in temperature is said to have a high viscosity index.
- a viscosity modifier usually a polymeric material, can be incorporated into a lubricant composition to increase the viscosity index of the lubricant composition and to improve its rheological properties and/or lubricating performance including viscosity performance.
- Dispersant viscosity index improvers can function in a lubricating oil such as an internal combustion engine oil to improve both viscosity and dispersant performance since they are polymeric materials that contain a polar or dispersing group such as e. g. a polystyrene-hydrogenated polyisoprene diblock copolymer to which is grafted N-vinylimidazole as disclosed in U.S. Pat. No. 6,083,888.
- High molecular weight diblock copolymers containing an aromatic block can function in an internal combustion engine lubricant oil to provide both viscosity and dispersancy performance such as e. g.
- diblock copolymers of polystyrene and hydrogenated polyisoprene that have a total molecular weight of 100,000 or 135,000 as disclosed in U.S. Pat. No. 6,303,550.
- a further disclosure in U.S. Pat. No. 6,303,550 is that low molecular weight diblock copolymers, containing a critical chain length of an aromatic block and preferably 60 weight % or greater of the aromatic block, can also provide dispersancy performance such as e. g. a polystyrene-hydrogenated polyisoprene diblock copolymer having a total molecular weight of 22,000; a molecular weight of 17,380 for the polystyrene block; and a 79% by weight polystyrene content.
- the present invention provides a lubricant composition
- a lubricant composition comprising a low molecular weight diblock copolymer having a low aromatic content where the diblock copolymer functions to provide performance as a viscosity modifier and unexpectedly as an effective dispersant in engine tests.
- This performance includes increasing the viscosity index and increasing the soot dispersion, which reduces undesirable soot-induced viscosity increase, of the lubricant in an internal combustion engine, especially a diesel engine that uses EGR.
- the dispersant performance of the diblock copolymer of this invention is unexpected since the diblock copolymers of earlier disclosures having dispersant performance are considerably higher in total molecular weight or have a considerably higher aromatic content.
- An object of the present invention is to provide lubricant and concentrate compositions that are useful in functional fluids.
- a further object of the invention is to provide lubricant and concentrate compositions that are useful in an internal combustion engine oil.
- a still further object of the invention is to provide a lubricant and concentrate compositions that are useful in a compression-ignited internal combustion engine oil
- An additional object of this invention is to provide lubricant and concentrate compositions that are useful in a compression-ignited internal combustion engine oil where the engine is equipped with an exhaust gas recirculation system.
- a lubricant composition comprises (A) a major amount of an oil of lubricating viscosity, and (B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block wherein the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight.
- a concentrate composition comprises a concentrate-forming amount of an oil of lubricating viscosity, and the above described diblock copolymer of component (B).
- a method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises incorporating into the lubricant composition a viscosity performance-improving amount of the above described diblock copolymer of component (B).
- a method for lubricating an internal combustion engine comprises supplying to the engine the above described lubricant composition comprising components (A) an oil of lubricating viscosity and (B) a diblock copolymer.
- the present invention comprises lubricant and concentrate compositions and methods thereof comprising a low molecular weight diblock copolymer of low aromatic content where the compositions and methods are useful in or as functional fluids to include for example an internal combustion engine oil lubricant, a power transmission fluid, an automotive or industrial gear oil, a farm tractor hydraulic fluid, a hydraulic fluid, a normally liquid fuel composition, a grease, and a metalworking fluid.
- the lubricant composition or concentrate composition are for an internal combustion engine, a spark-ignited internal combustion engine, a compression-ignited internal combustion engine, or a compression-ignited internal combustion engine having an exhaust gas recirculation system.
- the invention can comprise a lubricant composition comprising (A) a major amount of an oil of lubricating viscosity, and (B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block wherein the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight
- the oil of lubricating viscosity of component (A) can comprise a natural oil, a synthetic oil, or a mixture thereof.
- the oil of lubricating viscosity can have a kinematic viscosity in mm 2 /s (or centistokes) at 100° C. of 2-70, and in other instances of 3-50, or 4-40.
- Natural oils can comprise crude and refined mineral oils derived from petroleum, coal, shale, or a mixture thereof; animal oils; plant or vegetable oils; or a mixture thereof.
- Synthetic oils can comprise both unhydrogenated and hydrogenated polyolefins, carboxylic acid esters prepared from mono- and/or polycarboxylic acids or reactive equivalents thereof and from mono- and/or polyhydric alcohols, alkylated aromatics, polyglycols and derivatives thereof, phosphate esters, silicone oils, hydrocarbons prepared by a gas to liquid process such as for example a Fischer-Trospsch process, or a mixture thereof.
- the oil of lubricating viscosity can include the American Petroleum Institute Group I, II, III, IV and V base oils.
- the oil of lubricating viscosity can be present in the lubricant composition of the present invention in a major amount, and in other embodiments can be present in the lubricant composition on a weight basis at greater than 50%, at 60 to 99.9%, at 70 to 99.5%, or at 80 to 95%.
- the copolymer of component (B) of this invention can comprise a polymer from at least one monovinyl aromatic hydrocarbon monomer and at least one conjugated diene monomer.
- the copolymer can comprise a) a random copolymer formed by polymerization of a mixture of at least one monovinyl aromatic hydrocarbon and at least one conjugated diene, b) a block copolymer formed by sequential polymerization of the at least one monovinyl aromatic hydrocarbon and the at least one conjugated diene, or c) a mixture thereof.
- the block copolymer can comprise one or more blocks of at least one monovinyl aromatic hydrocarbon and one or more blocks of at least one conjugated diene.
- the copolymer of component (B) comprises a diblock copolymer comprising a poly(vinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block.
- the vinyl aromatic hydrocarbon of the poly(vinyl aromatic hydrocarbon) block can be a single monomer or can be a mixture of two or more monomers.
- the conjugated diene of the poly(conjugated diene) block can be a single monomer or a mixture of two or more monomers.
- the diblock copolymer of component (B) is derived from a single monovinyl aromatic hydrocarbon monomer and a single conjugated diene monomer.
- the monovinyl aromatic hydrocarbon monomer of the copolymer of component (B) can comprise any vinyl-substituted aromatic hydrocarbon, and in other instances can comprise vinyl-substituted aromatic hydrocarbons having 8 to 18 carbon atoms, or 8 to 13 carbon atoms.
- the monovinyl aromatic hydrocarbon can comprise for example styrene; an alkyl-substituted styrene such as for example alpha-methylstyrene, 3- and/or 4-methylstyrene, alpha,2-dimethylstyrene, and 2,4-dimethylstyrene; an alkoxy-substituted styrene such as for example 2-, 3- and 4-vinylanisole and beta-methoxystyrene; a vinylnaphthalene such as for example 1- and 2-vinylnaphthalene; an alkyl-substituted vinylnaphthalene; or a mixture thereof.
- styrene an alkyl-substituted styrene such as for example alpha-methylstyrene, 3- and/or 4-methylstyrene, alpha,2-dimethylstyrene, and 2,4-dimethylstyrene
- the monovinyl aromatic hydrocarbon can have one or more alkyl and/or alkoxy substituents, and the alkyl and/or alkoxy substituents can contain 1 or more carbon atoms and usually contain 1 to 6 carbon atoms.
- the monovinyl aromatic hydrocarbon is selected from the group consisting of styrene, an alkyl-substituted styrene, an alkoxy-substituted styrene, and a mixture thereof.
- the monovinyl aromatic hydrocarbon is selected from the group consisting of styrene, alpha-methylstyrene, a vinylanisole, and a mixture thereof.
- the conjugated diene monomer of the copolymer of component (B) can comprise any conjugated diene, and in other instances can comprise a conjugated diene having 4 to 24 carbon atoms, 4 to 8 carbon atoms, 4 to 8 carbon atoms, or 4 to 6 carbon atoms.
- the conjugated diene can comprise for example a butadiene such as for example 1,3-butadiene and isoprene; a pentadiene such as piperylene (usually a mixture of cis and trans isomers) and 4-methyl-1,3-pentadiene; a hexadiene such as 1,3- and 2,4-hexadiene and 2,5-dimethyl-2,4-hexadiene; an octadiene such as 1,3-octadiene; or a mixture thereof.
- the conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, piperylene, and a mixture thereof.
- the monovinyl aromatic hydrocarbon is styrene and the conjugated diene is isoprene or 1,3-butadiene or a mixture thereof.
- the monovinyl aromatic hydrocarbon and conjugated diene monomers of this invention are available from numerous manufacturers and chemical suppliers. Both the random copolymer and block copolymer can be prepared by well known procedures including by an anionic living polymerization using an alkali metal or alkali metal compound as a catalyst such as for example an organo alkali metal like a butyllithium. While the random copolymer is formed by polymerizing a mixture of the monomers, a block copolymer is formed by polymerizing a first monomer or monomers such as for example styrene to form a first polymer block followed by polymerization onto the first polymer block of a second monomer or monomers such as isoprene to form a second polymer block.
- the polymerization can be run at ⁇ 20 to 120° C., and in other instances at 0 to 100° C., or at 20 to 80° C.
- the polymerization can be run in the presence of an inert solvent to include a nonpolar solvent such as a hydrocarbon like cyclohexane or a mixed nonpolar/polar solvent such as a mixture of a hydrocarbon and an ether.
- the random or block copolymer can then be selectively hydrogenated to reduce olefinic unsaturation by well known methods such as hydrogenation using a reduced nickel on kieselguhr catalyst.
- the hydrogenation can reduce at least 90% of the olefinic unsaturation, and in other instances at least 95% or at least 98% of the olefinic unsaturation can be reduced.
- U.S. Pat. No. 3,554,911 describes procedures for preparing a copolymer using an anionic catalyst and for selectively hydrogenating the copolymer.
- the diblock copolymer of component (B) of this invention can have a weight average molecular weight, based on gel permeation chromatography measurements using a polystyrene standard, of 10,000 to 50,000, and in other embodiments can have a weight average molecular weight of 12,000 to 47,000; 14,000 to 44,000; 10,000 to 25,000; or 25,000 to 50,000.
- the diblock copolymer of component (B) can have a poly(monovinyl aromatic hydrocarbon) content on a weight basis of 5 to 55%, and in other embodiments can have a poly(monovinyl aromatic hydrocarbon) content of 5 to 45%, 16 to 43%, or 27 to 41%.
- the diblock copolymer of component (B) can be present in a lubricant composition of this invention in a minor amount, and in other embodiments can be present in the lubricant composition on a weight basis at less than 50%, at 0.1 to 20%, at 0.1 to 10%, at 0.2 to 6%, or at 0.2 to 3%.
- the lubricant composition of the present invention can further comprise (C) at least one other additive.
- the other additive or additives are normally selected based on what type of functional fluid use the lubricant composition is intended for.
- Additives generally useful in various functional fluids, to include lubricant compositions for an internal combustion engine can comprise at least one additive selected from the group consisting of a dispersant; an antiwear agent; an antioxidant; a detergent; a corrosion inhibitor to include for example an alkenylsuccinic acid, tolyltriazole or a derivative thereof, and dimercaptothiadiazole or a derivative thereof; an antifoam agent to include for example a silicone oil and a polyacrylate; a pour point depressant to include for example an esterified copolymer of maleic anhydride and styrene, and a polymethacrylate; a viscosity modifier that is different from component (B); a friction modifier to include for example a vegetable oil, an ester and amide of
- the lubricant composition further comprises (C) at least one other additive selected from the group consisting of a dispersant, an antiwear agent, an antioxidant, a detergent, a corrosion inhibitor, an antifoam agent, a pour point depressant, and a viscosity modifier that is different from component (B).
- the detergent can comprise a neutral or basic metal salt, usually where the metal is an alkali or alkaline earth metal, of an alkylarylsulfonic acid; an alkylphenol, a formaldehyde coupled alkylphenol, a sulfur coupled alkylphenol, or a mixture thereof; an aliphatic or aromatic carboxylic acid having 12 or more carbon atoms; or a mixture thereof.
- a neutral or basic metal salt usually where the metal is an alkali or alkaline earth metal, of an alkylarylsulfonic acid; an alkylphenol, a formaldehyde coupled alkylphenol, a sulfur coupled alkylphenol, or a mixture thereof; an aliphatic or aromatic carboxylic acid having 12 or more carbon atoms; or a mixture thereof.
- the dispersant can comprise a hydrocarbyl-substituted succinimide and/or a hydrocarbyl-substituted succinate ester where the hydrocarbyl group has a number average molecular weight of 700 to 3,000 and the succinimide or succinate is prepared from a polyamine, to include polyethylenepolyamines, and/or a mono- or polyhydric alcohol, to include pentaerythritol; a Mannich base; a hydrocarbyl-substituted amine derived from a hydrocarbyl group having a number average molecular weight of 700 to 3,000; or a mixture thereof.
- the hydrocarbyl group of the dispersant is a univalent group that is predominately hydrocarbon in nature but it can contain heteroatoms, to include oxygen and halogens, in the main carbon chain or in chains or groups attached to the main carbon chain.
- the dispersant comprises a reaction product of a hydrocarbyl-substituted succinic acylating agent and a polyethylenepolyamine wherein the hydrocarbyl substituent is derived from a polyisobutylene, and the dispersant reaction product has a nitrogen to carbonyl ratio that is greater than 1.
- the polyisobutylene of the dispersant reaction product can have a number average molecular weight of 700 to 3,000; 900 to 2,500; or 1,300 to 2,500.
- the number of succinic acylating groups per hydrocarbyl group in the dispersant reaction product can be 0.8 to 2, 1.1 to 2, or 1.5 to 2.
- the succinic acylating group of the dispersant reaction product can be a succinic anhydride group or a reactive equivalent thereof to include a succinic acid group or succinate ester group.
- the dispersant reaction product can have a TBN, total base number expressed in milligram equivalents of KOH per gram of sample, of 25 to 70, 30 to 65, or 35 to 60.
- the dispersant to include the above described dispersant reaction product can be present in the lubricant composition on a weight basis at I to 12%, at 2 to 10%, or at 2 to 8%.
- the viscosity modifier is generally a polymeric material and can comprise a viscosity index improver, a dispersant viscosity modifier that usually contains a polar group incorporated either via polymerization of a monomer or by grafting and that can improve both the viscosity index and dispersancy of a lubricant composition, or a mixture thereof.
- the viscosity modifier can comprise an olefin homopolymer such as a polyisobutylene; an olefin copolymer such as an ethylene-propylene copolymer or ethylene-propylene-diene copolymer; an acrylate homopolymer or copolymer; a methacrylate homopolymer or copolymer such as a copolymer of 2 or more methacrylate esters from 2 or more alcohols differing in carbon number and/or branching; a maleic anhydride-styrene copolymer or a derivative thereof such as an amine salt of a partially esterified copolymer of maleic anhydride and styrene; a hydrogenated styrene-diene copolymer such as a copolymer of styrene and 1,3-butadiene; or a mixture thereof.
- an olefin homopolymer such as a polyisobutylene
- the dispersant viscosity modifier can comprise functionalized forms of the above described viscosity modifier that through the functionalization contain polar groups to include for example basic amino groups such as a diphenylamine group that can provide, in addition to viscosity performance, dispersant and/or antioxidation performance.
- the functionalization can be done by including a polar monomer in the polymerization to form the viscosity modifier, by grafting a polar reagent onto the viscosity modifier, by reaction of a polar reagent with a reactive group on the viscosity modifier, or a mixture thereof.
- component (C) comprises a viscosity modifier other than component (B), a dispersant viscosity modifier, or a mixture thereof.
- the antioxidant can comprise at least one member selected from the group consisting of a diarylamine to include an alkylated diphenylamine; a hindered phenol to include a base catalyzed addition product of 2,6-di-t-butylphenol and an alkyl acrylate ester; a sulfurized olefinic compound to, include a sulfurized olefin, a sulfurized olefin containing carboxylate ester, a sulfurized olefin containing triglyceride, or a mixture thereof.
- the antiwear agent can comprise an organic phosphate to include a metal salt of a dialkyl dithiophosphate; a sulfurized olefinic compound as described above under the antioxidant; a dithiocarbamate to include a molybdenum dithiocarbamate; or a mixture thereof.
- the antiwear agent can comprise a metal salt of a dialkyl dithiophosphate where the dialkyl dithiophosphate is derived from one or more primary alcohols, from one or more secondary alcohols, or from a mixture of one or more primary alcohols and one or more secondary alcohols.
- additives of component (C) are well known and are available commercially and/or can be prepared by known procedures.
- U.S. Pat. No. 4,904,401 discloses several of the additives of component (C) to include procedures for their preparation.
- Each of the additives of component (C) can be present in the lubricant composition on a weight basis at 0.001 to 14%; and in other instances at 0.001 to 11%, or at 0.001 to 8%.
- the lubricant composition can have on a weight basis a sulfated ash content of greater than 1.3%, 1.3% or less, 1.2% or less, or 1.1% or less; can have on a weight basis a sulfur content of greater than 0.5%, 0.5% or less, 0.4% or less, or 0.3% or less; and can have on a weight basis a phosphorus content of greater than 0.14%, 0.14% or less, 0.13% or less, or 0.12% or less.
- lubricant additives of components (B) and (C) can be added directly to a lubricant composition of this invention, however they are normally combined with component (A), an oil of lubricating of lubricating viscosity, to form one or more concentrate compositions.
- a concentrate composition provides a concentrated form of the lubricant composition that has a higher lubricant additive content.
- a concentrate composition is handleable and transferable, more economical to ship, and readily blended with additional oil and optionally with additional additives, additional concentrates, or a mixture thereof to form a lubricant composition.
- a concentrate composition comprises a concentrate-forming amount of an oil of lubricating viscosity of component (A) and a diblock copolymer of component (B).
- the concentrate composition can further comprise at least one other additive of component (C).
- the concentrate composition can have a concentrate-forming amount of an oil of lubricating viscosity, and in other instances can have an amount of an oil of lubricating viscosity on a weight basis of 15 to 75%, 25 to 65%, 35 to 55%, or 55 to 95%.
- the concentrate composition can have an amount of component (B) or components (B) and (C) on a weight basis of 25 to 85%, 35 to 75%, 45 to 65%, or 5 to 45%.
- the lubricant composition of the present invention can be prepared by admixing the components.
- the lubricant composition can be prepared by admixing components (A) and (B) or by further admixing component (C) with components (A) and (B).
- the lubricant composition can be prepared by admixing component (A) and a concentrate composition comprising component (B) or by further admixing one or more additives of component (C), one or more concentrate compositions comprising component (C), or a mixture thereof with component (A) and a concentrate composition comprising component (B).
- the lubricant and concentrate compositions of the invention are usually prepared by admixing the components with a mixing device from ambient to an elevated temperature of 100° C., 90° C., or 80° C.
- a method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises incorporating into the lubricant composition a viscosity performance-improving amount of the diblock copolymer of component (B) where the lubricant composition comprises a major amount of an oil of lubricating viscosity of component (A).
- the performance-improving amount of the diblock copolymer of component (B) can be an amount as described above in paragraph [0027].
- the improvement in viscosity performance of a lubricant composition for an internal combustion engine can comprise a reduction in soot-induced viscosity increase, an increase in the viscosity index, or a combination thereof.
- the internal combustion engine can be a compression-ignited or spark-ignited engine.
- the compression-ignited engine can be equipped with an exhaust gas recirculation system.
- the method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises a MackTM T-11 diesel engine having an exhaust gas recirculation system and the improvement in viscosity performance is a prevention or reduction in soot-induced viscosity increase.
- a nitrogen-containing dispersant is partially replaced with a diblock copolymer of component (B) to improve viscosity performance of a lubricant composition for an internal combustion engine which further improves lubricant performance by reducing corrosion of metal bearings and/or increases durability of seals.
- a method for lubricating an internal combustion engine comprises supplying to the engine a lubricant composition comprising a major amount of an oil of lubricating viscosity of component (A) and a minor amount of a diblock copolymer of component (B) as described above in paragraphs [0022] through [0027].
- the lubricant composition can further comprise one or more other additives of component (C) as described above.
- the internal combustion engine can be a compression-ignited or spark-ignited engine.
- the compression-ignited engine can be equipped with an exhaust gas recirculation system.
- lubricant compositions are prepared and run for 252 hours in the MackTM T-11 engine test that uses exhaust gas recirculation to evaluate the ability of the lubricant to reduce soot-induced viscosity increase.
- samples of the lubricant are removed at 12 hour intervals, and the % by weight soot and kinematic viscosity at 100° C. are measured.
- Test results are reported as the amount of soot (% soot at kinematic viscosity increase or % soot @ kv incr) present in the lubricant when the viscosity (kinematic viscosity at 100° C.) of the lubricant increases significantly.
- a lubricant is improved in reducing soot-induced viscosity increase when it contains a greater amount of soot before its viscosity increases significantly compared to another lubricant.
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Abstract
A lubricant composition comprises (A) a major amount of an oil of lubricating viscosity and (B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block where the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight. A concentrate composition, a method for improving viscosity performance of a lubricant composition for an internal combustion engine, and a method for lubricating an internal combustion engine comprise the diblock copolymer which is especially useful for reducing soot-induced viscosity increase in a compression-ignited internal combustion engine equipped with an exhaust gas recirculation system.
Description
- 1. Field of the Invention
- The present invention involves lubricant and concentrate compositions and methods thereof that comprise a diblock copolymer. The compositions and methods of this invention are especially useful for improving viscosity performance in an internal combustion engine.
- 2. Description of the Related Art
- Compression-ignited internal combustion engines, also termed diesel engines, of the heavy duty type can use exhaust gas recirculation (EGR) in efforts to reduce engine exhaust emissions of substances, such as nitrogen oxides, that are being regulated for health and environmental concerns. Among the consequences of recirculating the exhaust gas through the engine are different soot structures and increased viscosity of the oil or lubricant composition of the engine at lower soot levels compared with engines without EGR. It is desirable that the oil or lubricant composition exhibit minimal viscosity increase such as for example less than 12 mm2/sec (cSt) at a soot loading of 6%.
- A lubricant composition that has less change in its viscosity with a change in temperature is said to have a high viscosity index. A viscosity modifier, usually a polymeric material, can be incorporated into a lubricant composition to increase the viscosity index of the lubricant composition and to improve its rheological properties and/or lubricating performance including viscosity performance.
- Anderson in U.S. Pat. No. 4,036,910 discloses block copolymers as viscosity index improvers for lubrication oils.
- Elliott in U.S. Pat. No. 4,073,737 discloses that hydrogenated copolymers of conjugated dienes and when desired a vinyl aromatic monomer are useful as oil additives.
- Sutherland in U.S. Pat. No. 6,083,888 discloses dispersant viscosity index improvers from a linear diblock copolymer or a radial copolymer wherein N-vinyl imidazole groups are grafted onto the copolymer.
- Wedlock et al. in U.S. Pat. No. 6,303,550 and Research Disclosure Journal No. 38644 disclose a lubricating oil composition comprising a di-block copolymer of poly(monovinyl aromatic hydrocarbon) and hydrogenated poly(conjugated diene) as a dispersant additive.
- Ritchie et al. in U.S. Pat. No. 6,715,473 disclose that soot induced kinematic viscosity increase of lubricating oil compositions for heavy duty diesel engines equipped with EGR systems operating in a condensing mode can be ameliorated by selection of viscosity modifier, lubricating oil flow improvers, detergents and dispersants.
- Dispersant viscosity index improvers can function in a lubricating oil such as an internal combustion engine oil to improve both viscosity and dispersant performance since they are polymeric materials that contain a polar or dispersing group such as e. g. a polystyrene-hydrogenated polyisoprene diblock copolymer to which is grafted N-vinylimidazole as disclosed in U.S. Pat. No. 6,083,888. High molecular weight diblock copolymers containing an aromatic block can function in an internal combustion engine lubricant oil to provide both viscosity and dispersancy performance such as e. g. diblock copolymers of polystyrene and hydrogenated polyisoprene that have a total molecular weight of 100,000 or 135,000 as disclosed in U.S. Pat. No. 6,303,550. A further disclosure in U.S. Pat. No. 6,303,550 is that low molecular weight diblock copolymers, containing a critical chain length of an aromatic block and preferably 60 weight % or greater of the aromatic block, can also provide dispersancy performance such as e. g. a polystyrene-hydrogenated polyisoprene diblock copolymer having a total molecular weight of 22,000; a molecular weight of 17,380 for the polystyrene block; and a 79% by weight polystyrene content.
- The present invention provides a lubricant composition comprising a low molecular weight diblock copolymer having a low aromatic content where the diblock copolymer functions to provide performance as a viscosity modifier and unexpectedly as an effective dispersant in engine tests. This performance includes increasing the viscosity index and increasing the soot dispersion, which reduces undesirable soot-induced viscosity increase, of the lubricant in an internal combustion engine, especially a diesel engine that uses EGR. The dispersant performance of the diblock copolymer of this invention is unexpected since the diblock copolymers of earlier disclosures having dispersant performance are considerably higher in total molecular weight or have a considerably higher aromatic content.
- An object of the present invention is to provide lubricant and concentrate compositions that are useful in functional fluids.
- A further object of the invention is to provide lubricant and concentrate compositions that are useful in an internal combustion engine oil.
- A still further object of the invention is to provide a lubricant and concentrate compositions that are useful in a compression-ignited internal combustion engine oil
- An additional object of this invention is to provide lubricant and concentrate compositions that are useful in a compression-ignited internal combustion engine oil where the engine is equipped with an exhaust gas recirculation system.
- Additional objects and advantages of the present invention will be set forth in the Detailed Description which follows and, in part, will be obvious from the Detailed Description or may be learned by the practice of the invention. The objects and advantages of the invention may be realized by means of the instrumentalities and combinations pointed out in the appended claims.
- To achieve the foregoing objects in accordance with the present invention as described and claimed in this application, a lubricant composition comprises (A) a major amount of an oil of lubricating viscosity, and (B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block wherein the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight.
- In an embodiment of the invention a concentrate composition comprises a concentrate-forming amount of an oil of lubricating viscosity, and the above described diblock copolymer of component (B).
- In another embodiment of this invention a method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises incorporating into the lubricant composition a viscosity performance-improving amount of the above described diblock copolymer of component (B).
- In a further embodiment of the invention a method for lubricating an internal combustion engine comprises supplying to the engine the above described lubricant composition comprising components (A) an oil of lubricating viscosity and (B) a diblock copolymer.
- The present invention comprises lubricant and concentrate compositions and methods thereof comprising a low molecular weight diblock copolymer of low aromatic content where the compositions and methods are useful in or as functional fluids to include for example an internal combustion engine oil lubricant, a power transmission fluid, an automotive or industrial gear oil, a farm tractor hydraulic fluid, a hydraulic fluid, a normally liquid fuel composition, a grease, and a metalworking fluid. In several embodiments of the invention the lubricant composition or concentrate composition are for an internal combustion engine, a spark-ignited internal combustion engine, a compression-ignited internal combustion engine, or a compression-ignited internal combustion engine having an exhaust gas recirculation system.
- The invention can comprise a lubricant composition comprising (A) a major amount of an oil of lubricating viscosity, and (B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block wherein the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight
- Oil of Lubricating Viscosity
- The oil of lubricating viscosity of component (A) can comprise a natural oil, a synthetic oil, or a mixture thereof. The oil of lubricating viscosity can have a kinematic viscosity in mm2/s (or centistokes) at 100° C. of 2-70, and in other instances of 3-50, or 4-40. Natural oils can comprise crude and refined mineral oils derived from petroleum, coal, shale, or a mixture thereof; animal oils; plant or vegetable oils; or a mixture thereof. Synthetic oils can comprise both unhydrogenated and hydrogenated polyolefins, carboxylic acid esters prepared from mono- and/or polycarboxylic acids or reactive equivalents thereof and from mono- and/or polyhydric alcohols, alkylated aromatics, polyglycols and derivatives thereof, phosphate esters, silicone oils, hydrocarbons prepared by a gas to liquid process such as for example a Fischer-Trospsch process, or a mixture thereof. The oil of lubricating viscosity can include the American Petroleum Institute Group I, II, III, IV and V base oils. The oil of lubricating viscosity can be present in the lubricant composition of the present invention in a major amount, and in other embodiments can be present in the lubricant composition on a weight basis at greater than 50%, at 60 to 99.9%, at 70 to 99.5%, or at 80 to 95%.
- Diblock Copolymer
- The copolymer of component (B) of this invention can comprise a polymer from at least one monovinyl aromatic hydrocarbon monomer and at least one conjugated diene monomer. The copolymer can comprise a) a random copolymer formed by polymerization of a mixture of at least one monovinyl aromatic hydrocarbon and at least one conjugated diene, b) a block copolymer formed by sequential polymerization of the at least one monovinyl aromatic hydrocarbon and the at least one conjugated diene, or c) a mixture thereof. The block copolymer can comprise one or more blocks of at least one monovinyl aromatic hydrocarbon and one or more blocks of at least one conjugated diene. In an embodiment of the invention the copolymer of component (B) comprises a diblock copolymer comprising a poly(vinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block. The vinyl aromatic hydrocarbon of the poly(vinyl aromatic hydrocarbon) block can be a single monomer or can be a mixture of two or more monomers. The conjugated diene of the poly(conjugated diene) block can be a single monomer or a mixture of two or more monomers. In another embodiment of the invention the diblock copolymer of component (B) is derived from a single monovinyl aromatic hydrocarbon monomer and a single conjugated diene monomer.
- The monovinyl aromatic hydrocarbon monomer of the copolymer of component (B) can comprise any vinyl-substituted aromatic hydrocarbon, and in other instances can comprise vinyl-substituted aromatic hydrocarbons having 8 to 18 carbon atoms, or 8 to 13 carbon atoms. The monovinyl aromatic hydrocarbon can comprise for example styrene; an alkyl-substituted styrene such as for example alpha-methylstyrene, 3- and/or 4-methylstyrene, alpha,2-dimethylstyrene, and 2,4-dimethylstyrene; an alkoxy-substituted styrene such as for example 2-, 3- and 4-vinylanisole and beta-methoxystyrene; a vinylnaphthalene such as for example 1- and 2-vinylnaphthalene; an alkyl-substituted vinylnaphthalene; or a mixture thereof. The monovinyl aromatic hydrocarbon can have one or more alkyl and/or alkoxy substituents, and the alkyl and/or alkoxy substituents can contain 1 or more carbon atoms and usually contain 1 to 6 carbon atoms. In an embodiment of the invention the monovinyl aromatic hydrocarbon is selected from the group consisting of styrene, an alkyl-substituted styrene, an alkoxy-substituted styrene, and a mixture thereof. In another embodiment of the invention the monovinyl aromatic hydrocarbon is selected from the group consisting of styrene, alpha-methylstyrene, a vinylanisole, and a mixture thereof.
- The conjugated diene monomer of the copolymer of component (B) can comprise any conjugated diene, and in other instances can comprise a conjugated diene having 4 to 24 carbon atoms, 4 to 8 carbon atoms, 4 to 8 carbon atoms, or 4 to 6 carbon atoms. The conjugated diene can comprise for example a butadiene such as for example 1,3-butadiene and isoprene; a pentadiene such as piperylene (usually a mixture of cis and trans isomers) and 4-methyl-1,3-pentadiene; a hexadiene such as 1,3- and 2,4-hexadiene and 2,5-dimethyl-2,4-hexadiene; an octadiene such as 1,3-octadiene; or a mixture thereof. In an embodiment of the invention the conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, piperylene, and a mixture thereof. In another embodiment of the invention the monovinyl aromatic hydrocarbon is styrene and the conjugated diene is isoprene or 1,3-butadiene or a mixture thereof.
- The monovinyl aromatic hydrocarbon and conjugated diene monomers of this invention are available from numerous manufacturers and chemical suppliers. Both the random copolymer and block copolymer can be prepared by well known procedures including by an anionic living polymerization using an alkali metal or alkali metal compound as a catalyst such as for example an organo alkali metal like a butyllithium. While the random copolymer is formed by polymerizing a mixture of the monomers, a block copolymer is formed by polymerizing a first monomer or monomers such as for example styrene to form a first polymer block followed by polymerization onto the first polymer block of a second monomer or monomers such as isoprene to form a second polymer block. The polymerization can be run at −20 to 120° C., and in other instances at 0 to 100° C., or at 20 to 80° C. The polymerization can be run in the presence of an inert solvent to include a nonpolar solvent such as a hydrocarbon like cyclohexane or a mixed nonpolar/polar solvent such as a mixture of a hydrocarbon and an ether. The random or block copolymer can then be selectively hydrogenated to reduce olefinic unsaturation by well known methods such as hydrogenation using a reduced nickel on kieselguhr catalyst. The hydrogenation can reduce at least 90% of the olefinic unsaturation, and in other instances at least 95% or at least 98% of the olefinic unsaturation can be reduced. U.S. Pat. No. 3,554,911 describes procedures for preparing a copolymer using an anionic catalyst and for selectively hydrogenating the copolymer.
- The diblock copolymer of component (B) of this invention can have a weight average molecular weight, based on gel permeation chromatography measurements using a polystyrene standard, of 10,000 to 50,000, and in other embodiments can have a weight average molecular weight of 12,000 to 47,000; 14,000 to 44,000; 10,000 to 25,000; or 25,000 to 50,000. The diblock copolymer of component (B) can have a poly(monovinyl aromatic hydrocarbon) content on a weight basis of 5 to 55%, and in other embodiments can have a poly(monovinyl aromatic hydrocarbon) content of 5 to 45%, 16 to 43%, or 27 to 41%. The diblock copolymer of component (B) can be present in a lubricant composition of this invention in a minor amount, and in other embodiments can be present in the lubricant composition on a weight basis at less than 50%, at 0.1 to 20%, at 0.1 to 10%, at 0.2 to 6%, or at 0.2 to 3%.
- Other Additives
- The lubricant composition of the present invention can further comprise (C) at least one other additive. The other additive or additives are normally selected based on what type of functional fluid use the lubricant composition is intended for. Additives generally useful in various functional fluids, to include lubricant compositions for an internal combustion engine, can comprise at least one additive selected from the group consisting of a dispersant; an antiwear agent; an antioxidant; a detergent; a corrosion inhibitor to include for example an alkenylsuccinic acid, tolyltriazole or a derivative thereof, and dimercaptothiadiazole or a derivative thereof; an antifoam agent to include for example a silicone oil and a polyacrylate; a pour point depressant to include for example an esterified copolymer of maleic anhydride and styrene, and a polymethacrylate; a viscosity modifier that is different from component (B); a friction modifier to include for example a vegetable oil, an ester and amide of a fatty acid such as glycerol monooleate and oleamide, and an organo molybdenum compound; and an extreme pressure agent to include for example a polysulfide of an olefin, and a phosphate ester or derivative thereof. In an embodiment of the invention the lubricant composition further comprises (C) at least one other additive selected from the group consisting of a dispersant, an antiwear agent, an antioxidant, a detergent, a corrosion inhibitor, an antifoam agent, a pour point depressant, and a viscosity modifier that is different from component (B).
- The detergent can comprise a neutral or basic metal salt, usually where the metal is an alkali or alkaline earth metal, of an alkylarylsulfonic acid; an alkylphenol, a formaldehyde coupled alkylphenol, a sulfur coupled alkylphenol, or a mixture thereof; an aliphatic or aromatic carboxylic acid having 12 or more carbon atoms; or a mixture thereof.
- The dispersant can comprise a hydrocarbyl-substituted succinimide and/or a hydrocarbyl-substituted succinate ester where the hydrocarbyl group has a number average molecular weight of 700 to 3,000 and the succinimide or succinate is prepared from a polyamine, to include polyethylenepolyamines, and/or a mono- or polyhydric alcohol, to include pentaerythritol; a Mannich base; a hydrocarbyl-substituted amine derived from a hydrocarbyl group having a number average molecular weight of 700 to 3,000; or a mixture thereof. The hydrocarbyl group of the dispersant is a univalent group that is predominately hydrocarbon in nature but it can contain heteroatoms, to include oxygen and halogens, in the main carbon chain or in chains or groups attached to the main carbon chain. In an embodiment of the invention the dispersant comprises a reaction product of a hydrocarbyl-substituted succinic acylating agent and a polyethylenepolyamine wherein the hydrocarbyl substituent is derived from a polyisobutylene, and the dispersant reaction product has a nitrogen to carbonyl ratio that is greater than 1. The polyisobutylene of the dispersant reaction product can have a number average molecular weight of 700 to 3,000; 900 to 2,500; or 1,300 to 2,500. The number of succinic acylating groups per hydrocarbyl group in the dispersant reaction product can be 0.8 to 2, 1.1 to 2, or 1.5 to 2. The succinic acylating group of the dispersant reaction product can be a succinic anhydride group or a reactive equivalent thereof to include a succinic acid group or succinate ester group. The dispersant reaction product can have a TBN, total base number expressed in milligram equivalents of KOH per gram of sample, of 25 to 70, 30 to 65, or 35 to 60. The dispersant to include the above described dispersant reaction product can be present in the lubricant composition on a weight basis at I to 12%, at 2 to 10%, or at 2 to 8%.
- The viscosity modifier is generally a polymeric material and can comprise a viscosity index improver, a dispersant viscosity modifier that usually contains a polar group incorporated either via polymerization of a monomer or by grafting and that can improve both the viscosity index and dispersancy of a lubricant composition, or a mixture thereof. The viscosity modifier can comprise an olefin homopolymer such as a polyisobutylene; an olefin copolymer such as an ethylene-propylene copolymer or ethylene-propylene-diene copolymer; an acrylate homopolymer or copolymer; a methacrylate homopolymer or copolymer such as a copolymer of 2 or more methacrylate esters from 2 or more alcohols differing in carbon number and/or branching; a maleic anhydride-styrene copolymer or a derivative thereof such as an amine salt of a partially esterified copolymer of maleic anhydride and styrene; a hydrogenated styrene-diene copolymer such as a copolymer of styrene and 1,3-butadiene; or a mixture thereof. The dispersant viscosity modifier can comprise functionalized forms of the above described viscosity modifier that through the functionalization contain polar groups to include for example basic amino groups such as a diphenylamine group that can provide, in addition to viscosity performance, dispersant and/or antioxidation performance. The functionalization can be done by including a polar monomer in the polymerization to form the viscosity modifier, by grafting a polar reagent onto the viscosity modifier, by reaction of a polar reagent with a reactive group on the viscosity modifier, or a mixture thereof. In an embodiment of the invention component (C) comprises a viscosity modifier other than component (B), a dispersant viscosity modifier, or a mixture thereof.
- The antioxidant can comprise at least one member selected from the group consisting of a diarylamine to include an alkylated diphenylamine; a hindered phenol to include a base catalyzed addition product of 2,6-di-t-butylphenol and an alkyl acrylate ester; a sulfurized olefinic compound to, include a sulfurized olefin, a sulfurized olefin containing carboxylate ester, a sulfurized olefin containing triglyceride, or a mixture thereof.
- The antiwear agent can comprise an organic phosphate to include a metal salt of a dialkyl dithiophosphate; a sulfurized olefinic compound as described above under the antioxidant; a dithiocarbamate to include a molybdenum dithiocarbamate; or a mixture thereof. In several embodiments of the invention the antiwear agent can comprise a metal salt of a dialkyl dithiophosphate where the dialkyl dithiophosphate is derived from one or more primary alcohols, from one or more secondary alcohols, or from a mixture of one or more primary alcohols and one or more secondary alcohols.
- The above described additives of component (C) are well known and are available commercially and/or can be prepared by known procedures. U.S. Pat. No. 4,904,401 discloses several of the additives of component (C) to include procedures for their preparation. Each of the additives of component (C) can be present in the lubricant composition on a weight basis at 0.001 to 14%; and in other instances at 0.001 to 11%, or at 0.001 to 8%.
- In several embodiments of this invention the lubricant composition can have on a weight basis a sulfated ash content of greater than 1.3%, 1.3% or less, 1.2% or less, or 1.1% or less; can have on a weight basis a sulfur content of greater than 0.5%, 0.5% or less, 0.4% or less, or 0.3% or less; and can have on a weight basis a phosphorus content of greater than 0.14%, 0.14% or less, 0.13% or less, or 0.12% or less.
- Concentrate Compositions
- The lubricant additives of components (B) and (C) can be added directly to a lubricant composition of this invention, however they are normally combined with component (A), an oil of lubricating of lubricating viscosity, to form one or more concentrate compositions. A concentrate composition provides a concentrated form of the lubricant composition that has a higher lubricant additive content. A concentrate composition is handleable and transferable, more economical to ship, and readily blended with additional oil and optionally with additional additives, additional concentrates, or a mixture thereof to form a lubricant composition. In an embodiment of the invention a concentrate composition comprises a concentrate-forming amount of an oil of lubricating viscosity of component (A) and a diblock copolymer of component (B). In another embodiment of the invention the concentrate composition can further comprise at least one other additive of component (C). The concentrate composition can have a concentrate-forming amount of an oil of lubricating viscosity, and in other instances can have an amount of an oil of lubricating viscosity on a weight basis of 15 to 75%, 25 to 65%, 35 to 55%, or 55 to 95%. The concentrate composition can have an amount of component (B) or components (B) and (C) on a weight basis of 25 to 85%, 35 to 75%, 45 to 65%, or 5 to 45%.
- Preparation of Compositions
- The lubricant composition of the present invention can be prepared by admixing the components. In several instances of the invention the lubricant composition can be prepared by admixing components (A) and (B) or by further admixing component (C) with components (A) and (B). In several other instances of the invention the lubricant composition can be prepared by admixing component (A) and a concentrate composition comprising component (B) or by further admixing one or more additives of component (C), one or more concentrate compositions comprising component (C), or a mixture thereof with component (A) and a concentrate composition comprising component (B). The lubricant and concentrate compositions of the invention are usually prepared by admixing the components with a mixing device from ambient to an elevated temperature of 100° C., 90° C., or 80° C.
- Method for Improving Performance
- In an embodiment of the invention a method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises incorporating into the lubricant composition a viscosity performance-improving amount of the diblock copolymer of component (B) where the lubricant composition comprises a major amount of an oil of lubricating viscosity of component (A). The performance-improving amount of the diblock copolymer of component (B) can be an amount as described above in paragraph [0027]. The improvement in viscosity performance of a lubricant composition for an internal combustion engine can comprise a reduction in soot-induced viscosity increase, an increase in the viscosity index, or a combination thereof. The internal combustion engine can be a compression-ignited or spark-ignited engine. The compression-ignited engine can be equipped with an exhaust gas recirculation system. In another embodiment of the invention the method for improving the viscosity performance of a lubricant composition for an internal combustion engine comprises a Mack™ T-11 diesel engine having an exhaust gas recirculation system and the improvement in viscosity performance is a prevention or reduction in soot-induced viscosity increase. In a further embodiment of the invention a nitrogen-containing dispersant is partially replaced with a diblock copolymer of component (B) to improve viscosity performance of a lubricant composition for an internal combustion engine which further improves lubricant performance by reducing corrosion of metal bearings and/or increases durability of seals.
- Method for Lubricating
- In another embodiment of this invention a method for lubricating an internal combustion engine comprises supplying to the engine a lubricant composition comprising a major amount of an oil of lubricating viscosity of component (A) and a minor amount of a diblock copolymer of component (B) as described above in paragraphs [0022] through [0027]. The lubricant composition can further comprise one or more other additives of component (C) as described above. The internal combustion engine can be a compression-ignited or spark-ignited engine. The compression-ignited engine can be equipped with an exhaust gas recirculation system.
- The following examples are provided to illustrate the invention, but are not intended to and should not be used to limit the scope of the invention.
- Mack™ T-11 EGR Test
- Four lubricant compositions are prepared and run for 252 hours in the Mack™ T-11 engine test that uses exhaust gas recirculation to evaluate the ability of the lubricant to reduce soot-induced viscosity increase. During each test run samples of the lubricant are removed at 12 hour intervals, and the % by weight soot and kinematic viscosity at 100° C. are measured. Test results are reported as the amount of soot (% soot at kinematic viscosity increase or % soot @ kv incr) present in the lubricant when the viscosity (kinematic viscosity at 100° C.) of the lubricant increases significantly. A lubricant is improved in reducing soot-induced viscosity increase when it contains a greater amount of soot before its viscosity increases significantly compared to another lubricant.
Example No. Composition1, wt % % Soot @ KV Incr6 1 (comparative) 3.6% Dispt + 0.75% VM2 4.0 2 (comparative) 3.6% Dispt + 0.85% VM3 6.4 3 (comparative) 4.7% Dispt + 0.78% VM4 5.0 4 4.7% Dispt + 1.47% VM5 6.4 - While the engine oil of comparative Example 2 containing a high molecular weight styrene-isoprene diblock copolymer reduces soot-induced viscosity increase compared to the baseline oil of comparative Example 1, the engine oil of invention Example 4 containing a low molecular weight, low styrene content styrene-isoprene diblock copolymer unexpectedly reduces soot-induced viscosity increase compared to the baseline oil of comparative Example 3. This improvement in viscosity performance is unexpected because prior disclosures teach that improved viscosity performance for soot-induced viscosity increase is obtained from diblock copolymers having a much higher molecular wt. or a much higher aromatic content compared to the invention diblock copolymer. Furthermore, this reduction in soot-induced viscosity increase by the invention diblock copolymer is unexpected because (1) the styrene block becomes more oil soluble having less tendency to adsorb on the surface of soot particles as its molecular weight decreases and (2) the isoprene block is less able to provide steric repulsion to prevent soot agglomeration and consequent viscosity increase as its molecular weight decreases. For these reasons, low molecular weight styrene-isoprene diblock copolymers would be expected to suspend or disperse soot poorly.
- Each of the documents referred to in this Detailed Description of the Invention section is incorporated herein by reference. All numerical quantities in this application used to describe or claim the present invention are understood to be modified by the word “about” except for the examples or where explicitly indicated otherwise. All chemical treatments or contents throughout this application regarding the present invention are understood to be as actives unless indicated otherwise even though solvents or diluents may be present.
Claims (18)
1. A lubricant composition, comprising;
(A) a major amount of an oil of lubricating viscosity; and
(B) a minor amount of a diblock copolymer comprising a poly(monovinyl aromatic hydrocarbon) block and a hydrogenated poly(conjugated diene) block wherein the diblock copolymer has a weight average molecular weight of 10,000 to 50,000 and a poly(monovinyl aromatic hydrocarbon) content of 5 to 45% by weight.
2. The lubricant composition of claim 1 wherein the monovinyl aromatic hydrocarbon is selected from the group consisting of styrene, an alkyl-substituted styrene, an alkoxy-substituted styrene, and a mixture thereof.
3. The lubricant composition of claim 1 wherein the conjugated diene is selected from the group consisting of 1,3-butadiene; isoprene; piperylene; and a mixture thereof.
4. The lubricant composition of claim 1 wherein the monovinyl aromatic hydrocarbon is styrene and the conjugated diene is isoprene or 1,3-butadiene.
5. The lubricant composition of claim 1 wherein the diblock copolymer has a weight average molecular weight of 12,000 to 47,000 and a poly(monovinyl aromatic hydrocarbon) content of 16 to 43% by weight.
6. The lubricant composition of claim 1 , further comprising:
(C) at least one other additive selected from the group consisting of a dispersant, an antiwear agent, an antioxidant, a detergent, a corrosion inhibitor, an antifoam agent, a pour point depressant, and a viscosity modifier that is different from component (B).
7. The lubricant composition of claim 6 wherein the lubricant composition is prepared by admixing the components.
8. The lubricant composition of claim 1 further comprising a dispersant wherein the dispersant comprises a reaction product of a hydrocarbyl-substituted succinic acylating agent and a polyethylenepolyamine wherein the hydrocarbyl substituent is derived from a polyisobutylene, and the dispersant reaction product has a nitrogen to carbonyl ratio that is greater than 1.
9. The lubricant composition of claim 1 further comprising an antiwear agent wherein the antiwear agent comprises a metal salt of a dialkyl dithiophosphate wherein the dialkyl dithiophosphate is derived from one or more secondary alcohols.
10. The lubricant composition of claim 1 further comprising an antioxidant wherein the antioxidant comprises at least one member selected from the group consisting of a hindered phenol, a diarylamine, and a sulfurized olefinic compound.
11. The lubricant composition of claim 1 further comprising a viscosity modifer wherein the viscosity modifier comprises an ethylene-propylene copolymer.
12. The lubricant composition of claim 1 wherein the lubricant composition has on a weight basis a sulfated ash content of 1.1% or less, a sulfur content of 0.5% or less, and a phosphorus content of 0.12% or less.
13. A concentrate composition, comprising:
a concentrate-forming amount of an oil of lubricating viscosity; and
component (B) of claim 1 .
14. A method for improving the viscosity performance of a lubricant composition for an internal combustion engine, comprising:
incorporating into the lubricant composition a viscosity performance-improving amount of component (B) of claim 1 wherein the lubricant composition comprises component (A).
15. The method of claim 14 wherein the engine is a compression-ignited internal combustion engine.
16. The method of claim 15 wherein the engine is equipped with an exhaust gas recirculation system.
17. A method for lubricating an internal combustion engine, comprising;
supplying to the engine the lubricant composition of claim 1 .
18. The method of claim 17 wherein the engine is a compression-ignited internal combustion engine.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US10/935,395 US20060052255A1 (en) | 2004-09-07 | 2004-09-07 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
EP05794118A EP1786889A1 (en) | 2004-09-07 | 2005-09-06 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
JP2007530460A JP2008512517A (en) | 2004-09-07 | 2005-09-06 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
CA002579318A CA2579318A1 (en) | 2004-09-07 | 2005-09-06 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
PCT/US2005/031609 WO2006029111A1 (en) | 2004-09-07 | 2005-09-06 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
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US10/935,395 US20060052255A1 (en) | 2004-09-07 | 2004-09-07 | Aromatic diblock copolymers for lubricant and concentrate compositions and methods thereof |
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US20070232503A1 (en) * | 2006-03-31 | 2007-10-04 | Haigh Heather M | Soot control for diesel engine lubricants |
WO2015027367A1 (en) * | 2013-08-30 | 2015-03-05 | 中国石油天然气股份有限公司 | Macromolecule friction modifier with two polar ends |
US10829709B2 (en) | 2014-01-02 | 2020-11-10 | Infineum International Limited | Viscosity index improver concentrates for lubricating oil compositions |
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EP2001983B1 (en) * | 2006-03-27 | 2015-02-18 | The Lubrizol Corporation | Lubricating compositions containing a styrene-butadiene diblock copolymer |
US20100256030A1 (en) * | 2009-04-06 | 2010-10-07 | Hartley Rolfe J | Lubricating Oil Composition |
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US4036910A (en) * | 1969-12-12 | 1977-07-19 | Shell Oil Company | Block copolymers as viscosity index improvers for lubrication oils |
US4073737A (en) * | 1976-04-19 | 1978-02-14 | Exxon Research & Engineering Co. | Hydrogenated copolymers of conjugated dienes and when desired a vinyl aromatic monomer are useful as oil additives |
US4418234A (en) * | 1981-12-16 | 1983-11-29 | Phillips Petroleum Company | Viscosity index improver soluble in synthetic poly(α-olefin) lubricants |
US4904404A (en) * | 1987-08-12 | 1990-02-27 | Texaco Inc. | Lubricating oil containing viscosity index improver |
US5703023A (en) * | 1991-12-24 | 1997-12-30 | Ethyl Corporation | Lubricants with enhanced low temperature properties |
US6083888A (en) * | 1997-09-16 | 2000-07-04 | Shell Oil Company | Dispersant viscosity index improvers |
US6303550B1 (en) * | 1998-11-06 | 2001-10-16 | Infineum Usa L.P. | Lubricating oil composition |
US20040235684A1 (en) * | 2001-06-29 | 2004-11-25 | Cook Stephen J. | Lubricant from water in oil emulsion with suspended solid base |
US6715473B2 (en) * | 2002-07-30 | 2004-04-06 | Infineum International Ltd. | EGR equipped diesel engines and lubricating oil compositions |
Cited By (6)
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US20070232503A1 (en) * | 2006-03-31 | 2007-10-04 | Haigh Heather M | Soot control for diesel engine lubricants |
WO2007126953A3 (en) * | 2006-03-31 | 2008-02-21 | Exxonmobil Res & Eng Co | Soot control for diesel engine lubricants |
US20130045905A1 (en) * | 2006-03-31 | 2013-02-21 | Exxonmobil Research And Engineering Company | Soot control for diesel engine lubricants |
US8642524B2 (en) * | 2006-03-31 | 2014-02-04 | Exxonmobil Research And Engineering Company | Soot control for diesel engine lubricants |
WO2015027367A1 (en) * | 2013-08-30 | 2015-03-05 | 中国石油天然气股份有限公司 | Macromolecule friction modifier with two polar ends |
US10829709B2 (en) | 2014-01-02 | 2020-11-10 | Infineum International Limited | Viscosity index improver concentrates for lubricating oil compositions |
Also Published As
Publication number | Publication date |
---|---|
EP1786889A1 (en) | 2007-05-23 |
CA2579318A1 (en) | 2006-03-16 |
JP2008512517A (en) | 2008-04-24 |
WO2006029111A1 (en) | 2006-03-16 |
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Owner name: LUBRIZOL CORPORATION, THE, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ABRAHAM, WILLIAM D.;COVITCH, MICHAEL J.;GALIC, MARY;REEL/FRAME:015779/0677;SIGNING DATES FROM 20040901 TO 20040903 |
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