EP3655510A1 - Method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil - Google Patents
Method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oilInfo
- Publication number
- EP3655510A1 EP3655510A1 EP18746440.9A EP18746440A EP3655510A1 EP 3655510 A1 EP3655510 A1 EP 3655510A1 EP 18746440 A EP18746440 A EP 18746440A EP 3655510 A1 EP3655510 A1 EP 3655510A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersant
- weight percent
- lubricating oil
- oil
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000003749 cleanliness Effects 0.000 title claims abstract description 48
- 239000002270 dispersing agent Substances 0.000 claims abstract description 218
- 239000000203 mixture Substances 0.000 claims abstract description 119
- 239000003921 oil Substances 0.000 claims abstract description 115
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 108
- 230000008719 thickening Effects 0.000 claims abstract description 70
- -1 succinate ester amides Chemical class 0.000 claims description 74
- 239000000654 additive Substances 0.000 claims description 59
- 239000003599 detergent Substances 0.000 claims description 51
- 238000012360 testing method Methods 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 238000010998 test method Methods 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229920000058 polyacrylate Chemical class 0.000 claims description 9
- 229920000193 polymethacrylate Chemical class 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 230000000994 depressogenic effect Effects 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000006078 metal deactivator Substances 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- 150000003443 succinic acid derivatives Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000003890 succinate salts Chemical class 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 93
- 239000002585 base Substances 0.000 description 78
- 239000002199 base oil Substances 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 150000002148 esters Chemical class 0.000 description 27
- 239000000463 material Substances 0.000 description 27
- 239000001993 wax Substances 0.000 description 26
- 238000009472 formulation Methods 0.000 description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 description 24
- 239000000314 lubricant Substances 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000003607 modifier Substances 0.000 description 15
- 229920013639 polyalphaolefin Polymers 0.000 description 15
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- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 229920002367 Polyisobutene Polymers 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
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- 239000011777 magnesium Substances 0.000 description 11
- 239000010705 motor oil Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000002956 ash Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 6
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 239000002530 phenolic antioxidant Substances 0.000 description 6
- 229940014800 succinic anhydride Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 5
- 150000003900 succinic acid esters Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- 238000005727 Friedel-Crafts reaction Methods 0.000 description 4
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- 229920000768 polyamine Polymers 0.000 description 4
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- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C10M129/72—Esters of polycarboxylic acids
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- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2203/1065—Naphthenic fractions used as base material
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- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2030/02—Pour-point; Viscosity index
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- C10N2030/04—Detergent property or dispersant property
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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
- C10N2030/52—Base number [TBN]
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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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
Definitions
- This disclosure relates to a method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil.
- This disclosure also relates to a lubricating oil having a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components.
- This disclosure further relates to a method for tuning deposit control and cleanliness performance in an engine lubricated with a lubricating oil, from poor to excellent deposit control and cleanliness performance.
- Lubricating oils for internal combustion engines contain in addition to at least one base lubricating oil, additives which enhance the performance of the lubricating oil.
- additives such as detergents, dispersants, friction reducers, viscosity modifiers, antioxidants, corrosion inhibitors, antiwear additives, pour point depressants, seal swell additives, and antifoam agents are used in lubricating oil compositions.
- Dispersants help keep these byproducts in solution, thus diminishing their deposit on metal surfaces.
- Dispersants may be ashless or ash-forming in nature. So called ashless dispersants are organic materials that form substantially no ash upon combustion.
- a known class of dispersants is the alkenylsuccinic derivatives, typically produced by the reaction of a long chain substituted alkenyl succinic compound, usually a substituted succinic anhydride, with a polyhydroxy or polyamino compound.
- the long chain group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
- Viscosity modifiers are also used in lubricating oil compositions. These additives provide lubricants with high and low temperature operability, and impart shear stability at elevated temperatures and acceptable viscosity at low temperatures. Viscosity modifiers are well known commercially and in the literature.
- Engine cleanliness is a critical performance attribute of modern engine lubricants.
- a well known engine cleanliness test is a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure. This cleanliness test is a performance defining test which is required for all engine lubricants carrying ACEA certification.
- Foimulations that fail the CEC L78-T-99 test procedure are typically reformulated in an attempt to find the particular base oil and additive concentrations needed to pass the CEC L78- T-99 test procedure. This reformulation effort can be quite cumbersome and complicated.
- This disclosure relates to a method of using a critical dispersant thickening ratio to improve the deposit controlling properties and cleanliness performance of engine lubricants.
- the critical dispersant thickening ratio is effectively the ratio of the thickening efficiency contribution of the dispersant to the thickening efficiency contribution of the viscosity modifier.
- the critical dispersant thickening ratio provides a simple method of determining whether the deposit controlling properties and cleanliness performance would be considered acceptable.
- the critical dispersant thickening ratio can also be used to tune deposit control and cleanliness performance, and improve cleanliness in a formulation which fails the CEC L78-T-99 test procedure.
- this disclosure relates in part to a method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil.
- the formulated oil comprises a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components.
- the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than about 0.33.
- the critical dispersant thickening ratio is determined in accordance with the formula:
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
- this disclosure also relates in part to a lubricating oil comprising a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components.
- the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than about 0.33.
- the critical dispersant thickening ratio is determined in accordance with the formula:
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
- this disclosure also relates in part to a method for tuning deposit control and cleanliness performance in an engine lubricated with a lubricating oil.
- the method comprises using as the lubricating oil a formulated oil, in which the formulated oil comprises a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components; and adjusting the amount of the at least one dispersant and the at least one viscosity modifier sufficient to provide a determined critical dispersant thickening ratio.
- the critical dispersant thickening ratio is determined in accordance with the formula:
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
- the amount of the at least one dispersant and the at least one viscosity modifier is sufficient to provide a critical dispersant thickening ratio of greater than about 0.33 in a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure.
- a critical dispersant thickening ratio can be employed to tune a lubricant formulation from poor to excellent cleanliness performance based solely on the critical dispersant thickening ratio, regardless of other additives/chemistry included in the lubricant formulation.
- Fig. 1 graphically shows a plot of an engine cleanliness test, namely a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure (y axis) and critical dispersant thickening ratios (x axis), in accordance with the Examples.
- Fig. 2 shows lubricating oil formulations prepared in accordance with the Examples, and also testing results from the formulations in accordance with the Examples.
- a method of using a critical dispersant thickening ratio to improve the deposit controlling properties and cleanliness performance of engine lubricants is provided.
- the critical dispersant thickening ratio is effectively the ratio of the thickening efficiency contribution of the dispersant to the thickening efficiency contribution of the viscosity modifier.
- the critical dispersant thickening ratio provides a simple method of determining whether the deposit controlling properties and cleanliness performance would be considered acceptable.
- the critical dispersant thickening ratio can also be used to tune deposit control and cleanliness performance, and improve cleanliness in a formulation which fails the CEC L78-T-99 test procedure.
- the critical dispersant thickening ratio is determined in accordance with the formula:
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
- cleanliness performance can be assessed by calculating the critical dispersant thickening ratio. For example, for each dispersant [Gn] in the formulated oil, multiply [Gn] by dV/d[Gn], and sum overall all n of these contributions: ⁇ [Gn]*dV/d[Gn]. Then, for each viscosity modifier [Bm] in the formulated oil, multiply [Bm] by dV/d[Bm], and sum over all m of these contributions: ⁇ [Bm]*dV/d[Bm].
- the amount of the at least one dispersant and the at least one viscosity modifier is sufficient to provide a critical dispersant thickening ratio of greater than about 0.33 in a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure.
- the critical dispersant thickening ratio is greater than about 0.33, or greater than about 0.40, or greater than about 0.47, or greater than about 0.50, or greater than about 0.60, or greater than about 0.70, or greater than about 0.75, or greater than about 0.80, or greater than about 0.90, or greater than about 1.0.
- the critical dispersant thickening ratio can be used to improve mid-SAPS (sulfated ash, phosphorus and sulfur) light duty engine oil performance in a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure.
- Illustrative lubricating oil base stocks useful in this disclosure include, for example, Group I base stocks, Group II base stocks, Group III base stocks, Group IV base stocks, Group V base stocks, or mixtures thereof. Illustrative lubricating oil base stocks useful in this disclosure are described more fully hereinbelow.
- Illustrative dispersants useful in this disclosure include, for example, hydrocarbyl- substituted succinic acid derivatives, hydrocarbyl-substituted succinic anhydride derivatives, succinimides, succinate esters, succinate ester amides, Mannich base adducts derived from a hydrocarbyl-substituted phenol condensed with an aldehyde and an amine, hydrocarbyl-substituted amines, polymethacrylate or polyacrylate derivatives, and the like.
- the dispersant is an ashless dispersant.
- Illustrative dispersants useful in this disclosure are described more fully hereinbelow.
- Illustrative viscosity modifiers useful in this disclosure include, for example, linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, alkylated styrenes, and the like. Illustrative viscosity modifiers useful in this disclosure are described more fully hereinbelow.
- the lubricating oil can have other additives, for example, an antioxidant, detergent, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
- additives for example, an antioxidant, detergent, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
- Illustrative additives useful in this disclosure are described more fully hereinbelow.
- the critical dispersant thickening ratio can be employed to tune a lubricant formulation from poor to excellent cleanliness performance based solely on the critical dispersant thickening ratio, regardless of other additives/chemistry included in the lubricant formulation.
- the lubricating oil base stock is present in an amount from about 78 weight percent to about 98 weight percent
- the dispersant is present in an amount from about 0.5 weight percent to about 12 weight percent
- the viscosity modifier is present in an amount from about 0.5 weight percent to about 10 weight percent, based on the total weight of the lubricating oil.
- the amount of the dispersant and the viscosity modifier can be adjusted so as to tune the critical dispersant thickening ratio to a desired value.
- concentrations of base oils, dispersants and viscosity modifiers useful in this disclosure are described more fully hereinbelow.
- a method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil.
- the formulated oil comprises a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components.
- the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than about 0.33.
- the critical dispersant thickening ratio is determined in accordance with the formula described hereinabove.
- a lubricating oil comprising a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components.
- the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than about 0.33.
- the critical dispersant thickening ratio is determined in accordance with the formula described hereinabove.
- the lubricating oils of this disclosure preferably have less than or equal to 1% ash (by mass), more preferably less than or equal to 1% sulfated ash (by mass).
- a method for tuning deposit control and cleanliness performance in an engine lubricated with a lubricating oil.
- the method comprises using as the lubricating oil a formulated oil, said formulated oil comprising a lubricating oil base stock as a major component, and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components; and adjusting the amount of the at least one dispersant and the at least one viscosity modifier sufficient to provide a determined critical dispersant thickening ratio.
- the critical dispersant thickening ratio is determined in accordance with the formula described hereinabove.
- the amount of the at least one dispersant and the at least one viscosity modifier can be adjusted so as to tune the critical dispersant thickening ratio to a desired value.
- the amount of the at least one dispersant and the at least one viscosity modifier can be adjusted so as to tune the critical dispersant thickening ratio from a value less than about 0.33 (i.e., low performers as shown in Fig. 1) to a value greater than about 0.33 (i.e., intermediate and high performers as shown in Fig. 1).
- the lubricating oil of this disclosure is a passenger vehicle engine oil (PVEO) or a commercial vehicle engine oil (CVEO).
- PVEO passenger vehicle engine oil
- CVEO commercial vehicle engine oil
- Lubricating Oil Base Stocks A wide range of lubricating oils is known in the art. Lubricating oils that are useful in the present disclosure are both natural oils and synthetic oils. Natural and synthetic oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification.
- Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve the at least one lubricating oil property.
- One skilled in the art is familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation. Rerefined oils are obtained by processes analogous to refined oils but using an oil that has been previously used as a feed stock.
- Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
- Group I base stocks generally have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and less than about 90% saturates.
- Group ⁇ base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
- Group III stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03%) sulfur and greater than about 90% saturates.
- Group IV includes polyalphaolefins (PAO).
- Group V base stocks include base stocks not included in Groups I-IV. Table 1 below summarizes properties of each of these five groups.
- Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present disclosure. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
- Group II and/or Group III hydroprocessed or hydrocracked base stocks, as well as synthetic oils such as polyalphaolefins, alkyl aromatics and synthetic esters, i.e. Group IV and Group V oils are also well known base stock oils.
- Synthetic oils include hydrocarbon oil.
- Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example).
- Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
- PAOs derived from C8, CIO, CI 2, C14 olefins or mixtures thereof may be utilized. See U. S. Patent Nos. 4,956, 122; 4,827,064; and 4,827,073.
- the number average molecular weights of the PAOs typically vary from about 250 to about 3,000, although PAO's may be made in viscosities up to about 150 cSt (100°C).
- the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins which include, but are not limited to, C2 to about C32 alphaolefins with the C8 to about C16 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like, being preferred.
- the preferred polyalphaolefins are poly- 1-octene, poly- 1-decene and poly- 1-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
- the dimers of higher olefins in the range of C12 to C18 may be used to provide low viscosity base stocks of acceptably low volatility.
- the PAOs may be predominantly dimers, trimers and tetramers of the starting olefins, with minor amounts of the lower and/or higher oligomers, having a viscosity range of 1.5 cSt to 12 cSt.
- PAO fluids of particular use may include 3 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof. Mixtures of PAO fluids having a viscosity range of 1.5 cSt to approximately 150 cSt or more may be used if desired. Unless indicated otherwise, all viscosities cited herein are measured at 100°C.
- the PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
- a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
- a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boro
- Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer- Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof.
- Fischer- Tropsch waxes the high boiling point residues of Fischer- Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
- the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LF£DC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
- an amorphous hydrocracking/hydroisomerization catalyst such as one of the specialized lube hydrocracking (LF£DC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
- LF£DC specialized lube hydrocracking
- a crystalline hydrocracking/hydroisomerization catalyst preferably a zeolitic catalyst.
- ZSM-48 as described in U.S. Patent No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety. Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes
- Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax- derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at 100°C of about 2 cSt to about 50 cSt, preferably about 2 cSt to about 30 cSt, more preferably about 3 cSt to about 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0 cSt at 100°C and a viscosity index of about 141.
- Gas-to-Liquids (GTL) base oils may have useful pour points of about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower.
- Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301 ; 6,090,989, and 6, 165,949 for example, and are incorporated herein in their entirety by reference.
- the hydrocarbyl aromatics can be used as a base oil or base oil component and can be any hydrocarbyl molecule that contains at least about 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives.
- These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl biphenyls, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like.
- the aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like.
- the aromatic can be mono- or poly-functionalized.
- the hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups.
- the hydrocarbyl groups can range from about C6 up to about C60 with a range of about C8 to about C20 often being preferred. A mixture of hydrocarbyl groups is often preferred, and up to about three such substituents may be present.
- the hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents.
- the aromatic group can also be derived from natural (petroleum) sources, provided at least about 5% of the molecule is comprised of an above-type aromatic moiety. Viscosities at lOOoC of approximately 2 cSt to about 50 cSt are preferred, with viscosities of approximately 3 cSt to about 20 cSt often being more preferred for the hydrocarbyl aromatic component.
- an alkyl naphthalene where the alkyl group is primarily comprised of 1 -hexadecene is used.
- Other alkylates of aromatics can be advantageously used.
- Naphthalene or methyl naphthalene for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
- Alkylated naphthalene and analogues may also comprise compositions with isomeric distribution of alkylating groups on the alpha and beta carbon positions of the ring structure.
- Distribution of groups on the alpha and beta positions of a naphthalene ring may range from 100: 1 to 1 : 100, more often 50: 1 to 1 :50
- Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be about 2% to about 25%, preferably about 4% to about 20%, and more preferably about 4% to about 15%, depending on the application.
- Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963.
- an aromatic compound such as benzene or naphthalene
- an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964.
- catalysts are known to one skilled in the art.
- the choice of catalyst depends on the reactivity of the starting materials and product quality requirements.
- strong acids such as A1C13, BF3, or HF may be used.
- milder catalysts such as FeC13 or SnC14 are preferred.
- Newer alkylation technology uses zeolites or solid super acids.
- Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids.
- Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
- dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc
- esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n- hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
- Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl- 1,3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least about 4 carbon atoms, preferably C5 to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
- the hindered polyols such as the neopentyl polyol
- Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
- esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
- Engine oil formulations containing renewable esters are included in this disclosure.
- the renewable content of the ester is typically greater than about 70 weight percent, preferably more than about 80 weight percent and most preferably more than about 90 weight percent.
- Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
- Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non- mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
- GTL Gas-to-Liquids
- GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon- containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
- GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
- GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed
- GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at 100°C of from about 2 mm2/s to about 50 mm2/s (ASTM D445). They are further characterized typically as having pour points of -5°C to about -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of about 80 to about 140 or greater (ASTM D2270).
- the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
- the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
- GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
- the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
- the absence of phosphorus and aromatics make this materially especially suitable for the formulation of low SAP products.
- GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
- the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
- Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
- Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an "as-received" basis.
- Even in regard to the Group II stocks it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100 ⁇ VI ⁇ 120.
- the base stock component of the present lubricating oils will typically be from 1 to 99 weight percent of the total composition (all proportions and percentages set out in this specification are by weight unless the contrary is stated) and more preferably in the range of 10 to 99 weight percent, or more preferably from 15 to 80 percent, or more preferably from 20 to 70 percent, or more preferably from 25 to 60 percent, or more preferably from 30 to 50 percent.
- Dispersants 1 to 99 weight percent of the total composition (all proportions and percentages set out in this specification are by weight unless the contrary is stated) and more preferably in the range of 10 to 99 weight percent, or more preferably from 15 to 80 percent, or more preferably from 20 to 70 percent, or more preferably from 25 to 60 percent, or more preferably from 30 to 50 percent.
- Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
- Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature.
- the dispersant is ashless.
- So called ashless dispersants are organic materials that form substantially no ash upon combustion.
- non-metal-containing or borated metal-free dispersants are considered ashless.
- metal-containing detergents form ash upon combustion.
- Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
- the polar group typically contains at least one element of nitrogen or oxygen.
- Typical hydrocarbon chains contain 50 to 400 carbon atoms.
- a particularly useful class of dispersants are the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound.
- the long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
- Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U. S. patents describing such dispersants are U. S. Patent Nos.
- Hydrocarbyl-substituted succinic acid and hydrocarbyl -substituted succinic anhydride derivatives are useful dispersants.
- succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
- Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from about 1 : 1 to about 5: 1. Representative examples are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1,094,044. [0069] Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
- Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines.
- suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
- propoxylated hexamethylenediamine Representative examples are shown in U.S. Patent No. 4,426,305.
- the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more.
- the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.
- the above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
- Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Patent No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798, 165; and 3,803,039.
- Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxy aromatics or HNR2 group-containing reactants.
- Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084, 197.
- Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis- succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbyl ene group such as polyisobutylene having a Mn of from about 500 to about 5000, or from about 1000 to about 3000, or about 1000 to about 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.
- Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
- Polymethacrylate or polyacrylate derivatives are another class of dispersants. These dispersants are typically prepared by reacting a nitrogen containing monomer and a methacrylic or acrylic acid esters containing 5 -25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2, 100, 993, and 6,323, 164. Polymethacrylate and polyacrylate dispersants are normally used as multifunctional viscosity modifiers. The lower molecular weight versions can be used as lubricant dispersants or fuel detergents.
- Illustrative preferred dispersants useful in this disclosure include those derived from polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester, which dispersant has a polyalkenyl moiety with a number average molecular weight of at least 900 and from greater than 1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5, functional groups (mono- or dicarboxylic acid producing moieties) per polyalkenyl moiety (a medium functionality dispersant).
- Functionality (F) can be determined according to the following formula:
- SAP is the saponification number (i.e., the number of milligrams of KOH consumed in the complete neutralization of the acid groups in one gram of the succinic-containing reaction product, as determined according to ASTM D94); Mn is the number average molecular weight of the starting olefin polymer; and A.I. is the percent active ingredient of the succinic- containing reaction product (the remainder being unreacted olefin polymer, succinic anhydride and diluent).
- the polyalkenyl moiety of the dispersant may have a number average molecular weight of at least 900, suitably at least 1500, preferably between 1800 and 3000, such as between 2000 and 2800, more preferably from about 2100 to 2500, and most preferably from about 2200 to about 2400.
- the molecular weight of a dispersant is generally expressed in terms of the molecular weight of the polyalkenyl moiety. This is because the precise molecular weight range of the dispersant depends on numerous parameters including the type of polymer used to derive the dispersant, the number of functional groups, and the type of nucleophilic group employed.
- Polymer molecular weight can be determined by various known techniques.
- One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979).
- GPC gel permeation chromatography
- Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (e.g., ASTM D3592).
- the polyalkenyl moiety in a dispersant preferably has a narrow molecular weight distribution (MWD), also referred to as polydispersity, as determined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Ma).
- Mw weight average molecular weight
- Mo number average molecular weight
- Suitable polymers have a polydispersity of from about 1.5 to 2.1, preferably from about 1.6 to about 1.8.
- Suitable polyalkenes employed in the formation of the dispersants include homopolymers, interpolymers or lower molecular weight hydrocarbons.
- such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein Rl is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
- Another useful class of polymers is polymers prepared by cationic polymerization of monomers such as isobutene and styrene.
- monomers such as isobutene and styrene.
- Common polymers from this class include polyisobutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt.
- a preferred source of monomer for making poly-n-butenes is petroleum feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in U.S. Pat. No. 4,952,739.
- a preferred embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
- Polyisobutene polymers that may be employed are generally based on a polymer chain of from 1500 to 3000.
- the dispersant(s) are preferably non-polymeric (e.g., mono- or bis-succinimides). Such dispersants can be prepared by conventional processes such as disclosed in U. S. Patent Application Publication No. 2008/0020950, the disclosure of which is incorporated herein by reference.
- the dispersant(s) can be borated by conventional means, as generally disclosed in U.S. Patent Nos. 3,087,936, 3,254,025 and 5,430, 105.
- Such dispersants may be used in an amount of about 0.01 to 20 weight percent or 0.01 to 10 weight percent, preferably about 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. Or such dispersants may be used in an amount of about 2 to 12 weight percent, preferably about 4 to 10 weight percent, or more preferably 6 to 9 weight percent. On an active ingredient basis, such additives may be used in an amount of about 0.06 to 14 weight percent, preferably about 0.3 to 6 weight percent.
- the hydrocarbon portion of the dispersant atoms can range from C60 to C IOOO, or from C70 to C300, or from C70 to C200. These dispersants may contain both neutral and basic nitrogen, and mixtures of both.
- Dispersants can be end-capped by borates and/or cyclic carbonates.
- Nitrogen content in the finished oil can vary from about 200 ppm by weight to about 2000 ppm by weight, preferably from about 200 ppm by weight to about 1200 ppm by weight.
- Basic nitrogen can vary from about 100 ppm by weight to about 1000 ppm by weight, preferably from about 100 ppm by weight to about 600 ppm by weight.
- the dispersant concentrations are given on an “as delivered” basis.
- the active dispersant is delivered with a process oil.
- the "as delivered” dispersant typically contains from about 20 weight percent to about 80 weight percent, or from about 40 weight percent to about 60 weight percent, of active dispersant in the "as delivered" dispersant product.
- Viscosity modifiers also known as viscosity index improvers (VI improvers), and viscosity improvers
- VI improvers viscosity index improvers
- Viscosity modifiers can be included in the lubricant compositions of this disclosure.
- Viscosity modifiers provide lubricants with high and low temperature operability.
- Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters and viscosity modifier dispersants that function as both a viscosity modifier and a dispersant.
- Typical molecular weights of these polymers are between about 10,000 to 1,500,000, more typically about 20,000 to 1,200,000, and even more typically between about 50,000 and 1,000,000.
- suitable viscosity modifiers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
- Polyisobutylene is a commonly used viscosity modifier.
- Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
- Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
- Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation "PARATONE®” (such as “PARATONE® 8921” and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”); and from The Lubrizol Corporation under the trade designation "Lubrizol® 7067C”.
- Hydrogenated polyisoprene star polymers are commercially available from Infineum International Limited, e.g., under the trade designation "SV200”, “SV260”, “SV270” and “SV600”.
- Hydrogenated diene-styrene block copolymers are commercially available from Infmeum International Limited, e.g., under the trade designation "SV 150".
- the polymethacrylate or polyacrylate polymers can be linear polymers which are available from Evnoik Industries under the trade designation "Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation AstericTM (e.g., Lubrizol 87708 and Lubrizol 87725).
- Viscoplex® e.g., Viscoplex 6-954
- AstericTM e.g., Lubrizol 87708 and Lubrizol 87725.
- Illustrative vinyl aromatic-containing polymers useful in this disclosure may be derived predominantly from vinyl aromatic hydrocarbon monomer.
- Illustrative vinyl aromatic-containing copolymers useful in this disclosure may be represented by the following general formula:
- A is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer
- B is a polymeric block derived predominantly from conjugated diene monomer
- the viscosity modifiers may be used in an amount of less than about 10 weight percent, preferably less than about 7 weight percent, more preferably less than about 4 weight percent, and in certain instances, may be used at less than 2 weight percent, preferably less than about 1 weight percent, and more preferably less than about 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil.
- the viscosity modifier concentrations are given on an "as delivered” basis.
- the active polymer is delivered with a diluent oil.
- the "as delivered” viscosity modifier typically contains from 20 weight percent to 75 weight percent of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 weight percent to 20 weight percent of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the "as delivered” polymer concentrate.
- the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the commonly used lubricating oil performance additives including but not limited to detergents, corrosion inhibitors, rust inhibitors, metal deactivators, antiwear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
- the commonly used lubricating oil performance additives including but not limited to detergents, corrosion inhibitors, rust inhibitors, metal deactivators, antiwear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricity agents, anti-staining agents, chromophoric
- the total treat rates for the additives can range from 1 to 30 percent, or more preferably from 2 to 25 percent, or more preferably from 3 to 20 percent, or more preferably from 4 to 15 percent, or more preferably from 5 to 10 percent.
- Particularly preferred compositions have additive levels between 15 and 20 percent.
- Insoluble additives in oil can be dispersed in the lubricating oils of this disclosure.
- Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
- a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
- the anionic portion of the detergent is typically derived from an organic acid such as a sulfur-containing acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing acid, phenol, or mixtures thereof.
- the counterion is typically an alkaline earth or alkali metal.
- the detergent can be overbased as described herein.
- the detergent is preferably a metal salt of an organic or inorganic acid, a metal salt of a phenol, or mixtures thereof.
- the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof.
- the organic or inorganic acid is selected from an aliphatic organic or inorganic acid, a cycloaliphatic organic or inorganic acid, an aromatic organic or inorganic acid, and mixtures thereof.
- the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof. More preferably, the metal is selected from calcium (Ca), magnesium (Mg), and mixtures thereof.
- the organic acid or inorganic acid is preferably selected from a sulfur-containing acid, a carboxylic acid, a phosphorus-containing acid, and mixtures thereof.
- the metal salt of an organic or inorganic acid or the metal salt of a phenol comprises calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate, an overbased detergent, and mixtures thereof.
- Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
- TBN total base number
- Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
- Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates.
- the TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600.
- the TBN delivered by the detergent is between 1 and 20. More preferably between 1 and 12.
- Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates.
- a detergent mixture with a metal ratio of 1, in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
- Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2, for example) with an alkyl phenol or sulfurized alkylphenol.
- alkaline earth metal hydroxide or oxide Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2, for example
- Useful alkyl groups include straight chain or branched C1-C30 alkyl groups, preferably, C4-C20 or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
- starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent.
- the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
- metal salts of carboxylic acids are preferred detergents.
- carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
- Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
- Useful salicylates include long chain alkyl salicylates.
- One useful family of compositions is of the formula
- R is an alkyl group having 1 to about 30 carbon atoms
- n is an integer from 1 to
- M is an alkaline earth metal.
- R groups are alkyl chains of at least CI 1, preferably C13 or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function.
- M is preferably, calcium, magnesium, barium, or mixtures thereof. More preferably, M is calcium.
- Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Patent No. 3,595,791).
- the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
- Alkaline earth metal phosphates are also used as detergents and are known in the art.
- Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U. S. Patent No. 6,034,039.
- Preferred detergents include calcium sulfonates, magnesium sulfonates, calcium salicylates, magnesium salicylates, calcium phenates, magnesium phenates, and other related components (including borated detergents), and mixtures thereof.
- Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate.
- Overbased detergents are also preferred.
- the detergent concentration in the lubricating oils of this disclosure can range from about 0.5 to about 6.0 weight percent, preferably about 0.6 to 5.0 weight percent, and more preferably from about 0.8 weight percent to about 4.0 weight percent, based on the total weight of the lubricating oil.
- the detergent concentrations are given on an “as delivered” basis.
- the active detergent is delivered with a process oil.
- the "as delivered” detergent typically contains from about 20 weight percent to about 100 weight percent, or from about 40 weight percent to about 60 weight percent, of active detergent in the "as delivered" detergent product.
- Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
- One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U. S. Patent Nos. 4,798,684 and 5,084, 197, for example.
- Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C6+ alkyl groups and the alkylene coupled derivatives of these hindered phenols.
- phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
- Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
- Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
- ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4-octyl- 6-t-butyl-phenol); and 2,2'-bis(4-dodecyl-6-t-butyl-phenol).
- Para-coupled bisphenols include for example 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'-methylene-bis(2,6-di-t-butyl phenol).
- catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
- Catalytic antioxidants are more fully described in U.S. Patent No. 8, 048,833, herein incorporated by reference in its entirety.
- Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
- Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R8R9R10N where R8 is an aliphatic, aromatic or substituted aromatic group, R9 is an aromatic or a substituted aromatic group, and R10 is H, alkyl, aryl or Rl 1 S(0)XR12 where Rl 1 is an alkylene, alkenylene, or aralkylene group, R12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
- the aliphatic group R8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
- the aliphatic group is a saturated aliphatic group.
- both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
- Aromatic groups R8 and R9 may be joined together with other groups such as S.
- Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms.
- Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
- the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
- aromatic amine antioxidants useful in the present disclosure include: ⁇ , ⁇ '- dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
- Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
- Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent, more preferably zero to less than 1.5 weight percent, more preferably zero to less than 1 weight percent. Pour Point Depressants (PPDs)
- pour point depressants also known as lube oil flow improvers
- pour point depressants may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
- suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
- 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof.
- Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
- a metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate can be a useful component of the lubricating oils of this disclosure.
- ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
- ZDDP compounds generally are of the formula
- Rl and R2 are CI -CI 8 alkyl groups, preferably C2-C12 alkyl groups. These alkyl groups may be straight chain or branched.
- Alcohols used in the ZDDP can be propanol, 2- propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
- Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations "LZ 677A”, “LZ 1095” and “LZ 1371", from for example Chevron Oronite under the trade designation "OLOA 262" and from for example Afton Chemical under the trade designation "HITEC 7169".
- the ZDDP is typically used in amounts of from about 0.3 weight percent to about 1.5 weight percent, preferably from about 0.4 weight percent to about 1.2 weight percent, more preferably from about 0.5 weight percent to about 1.0 weight percent, and even more preferably from about 0.6 weight percent to about 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously.
- the ZDDP is a secondary ZDDP and present in an amount of from about 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
- Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
- Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.
- Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
- Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
- antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
- Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
- Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
- suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
- a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
- Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
- Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof.
- Illustrative organometallic friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Similar tungsten based compounds may be preferable.
- illustrative friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.
- Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.
- Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.
- Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono- stearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.
- Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-sterate, and the like.
- glycerol polyols these can include trimethylolpropane, pentaerythritol, sorbitan, and the like.
- esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters.
- Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like.
- the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
- Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers.
- the underlying alcohol portion can preferably be stearyl, myristyl, Cl l - C13 hydrocarbon, oleyl, isosteryl, and the like.
- the lubricating oils of this disclosure exhibit desired properties, e.g., wear control, in the presence or absence of a friction modifier.
- Useful concentrations of friction modifiers may range from 0.01 weight percent to 5 weight percent, or about 0.1 weight percent to about 2.5 weight percent, or about 0.1 weight percent to about 1.5 weight percent, or about 0.1 weight percent to about 1 weight percent. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or more, and often with a preferred range of 50-200 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
- Typical amounts of such additives useful in the present disclosure are shown in Table 2 below.
- Viscosity Modifier 0.1-10 0.1-1
- Anti-foam Agent 0.001-3 0.001-0.15
- additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
- the dispersants used in the formulations were polyisobutylsuccinimide/polyamine (PIBSA/PAM, PIB 1300 Mn) borated dispersant having a typical TBN of 26 mgKOH/g, a typical N content of 1.7%, and a typical B content of 0.87% (Dispersant 1); PIBSA/PAM (PIB 1300 Mn) borated dispersant having a typical TBN of 30 mgKOH/g, a typical N content of 1.57%, and a typical B content of 0.77% (Dispersant 2); PIBSA/PAM borated dispersant having a typical N content of 1.19%, and a typical B content of 2.3% (Dispersant 3); PIBSA/PAM dispersant having a typical N content of 1.43% (Dispersant 4); polyisobutenyl bis-succinimide (PIB 2300-2500 Mn) having a typical TBN of 28 mgKOH/g, and a typical N
- the viscosity modifiers used in the formulations were a hydrogenated isoprene star viscosity modifier having a Mw of 567k as determined by light scattering and a polydispersity index of 1.6 dissolved in a 4 cSt Fischer-Tropsch Group III base stock (Viscosity Modifier 1); a non-dispersant, styrene-isoprene star copolymer viscosity index improver having a Mp of about 825k (90%), a Mp of about 119k (10%), and 17% styrene dissolved in a 4 cSt Fischer-Tropsch Group III base stock (Viscosity Modifier 2); a solid styrene-isoprene block copolymer having a Mw of about 106k, a Mn of about 104k, and 33% styrene dissolved in a mixture of a 4 cSt Group IV base stock and TMP ester
- Base stocks used in the formulations were one or more of a Group I base stock, a Group II base stock, a Group III base stock, a Group IV base stock, a Group V base stock, or mixtures thereof.
- additives used in the formulations were one or more of an antioxidant, overbased detergent, pour point depressant, corrosion inhibitor, seal compatibility additive, anti-foam agent, inhibitor, anti-rust additive, and friction modifier (ashless).
- Cleanliness performance was assessed by calculating the critical dispersant thickening ratio as follows: (i) for each dispersant [Gn] in the formulated oil, multiply [Gn] by dV/d[Gn], and sum overall all n of these contributions: ⁇ [Gn]*dV/d[Gn]; (ii) for each viscosity modifier [Bm] in the formulated oil, multiply [Bm] by dV/d[Bm], and sum over all m of these contributions: ⁇ [Bm]*dV/d[Bm]; (iii) take the critical dispersant thickening ratio of ⁇ [Gn]*dV/d[Gn] over ⁇ [Bm]*dV/d[Bm], and add dispersant and/or remove viscosity modifier from the formulated oil if the critical dispersant thickening ratio is less than 0.33, and a superior passing CEC L78-T-99 test result is desired.
- Fig. 1 shows that above a critical dispersant thickening ratio of 0.47, a strong passing result in the VW TDi2 test is assured, while below a critical dispersant thickening ratio of 0.33, there are cleanliness concerns for the formulation.
- a method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil, said formulated oil comprising a lubricating oil base stock as a major component; and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components; wherein the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than 0.33; wherein the critical dispersant thickening ratio is determined in accordance with the formula:
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
- KvlOO kinematic viscosity
- the lubricating oil base stock comprises a Group I base stock, a Group II base stock, a Group III base stock, a Group IV base stock, a Group V base stock, or mixtures thereof
- the at least one dispersant is selected from the group consisting of hydrocarbyl -substituted succinic acid derivatives, hydrocarbyl-substituted succinic anhydride derivatives, succinimides, succinate esters, succinate ester amides, Mannich base adducts derived from a hydrocarbyl-substituted phenol condensed with an aldehyde and an amine, hydrocarbyl-substituted amines, and polymethacrylate or polyacrylate derivatives.
- the at least one viscosity modifier is selected from the group consisting of linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
- the lubricating oil further comprises one or more of an antioxidant, detergent, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
- a lubricating oil comprising a lubricating oil base stock as a major component; and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components; wherein the at least one dispersant and the at least one viscosity modifier are present in an amount sufficient to have a critical dispersant thickening ratio of greater than 0.33; wherein the critical dispersant thickening ratio is determined in accordance with the formula:
- [00161] 1 The lubricating oil of clause 10 wherein the amount of the at least one dispersant and the at least one viscosity modifier is sufficient to provide a critical dispersant thickening ratio of greater than 0.33 in a direct injection, ring sticking (rings 1 and 2), and piston cleanliness test using a Volkswagen TDI2 test engine, in accordance with CEC L78-T-99 test procedure.
- a method for tuning deposit control and cleanliness performance in an engine lubricated with a lubricating oil comprising:
- a formulated oil comprising a lubricating oil base stock as a major component; and a mixture of (i) at least one dispersant, and (ii) at least one viscosity modifier, as minor components; and
- [Gn] is the weight percent of each of n dispersants in the formulated oil
- [Bm] is the weight percent of each of m viscosity modifiers in the formulated oil
- dV/d[Gn] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of n dispersants in the formulated oil
- dV/d[Bm] is the kinematic viscosity (KvlOO) increase of the lubricating oil as determined by ASTM D445 per the weight percent of each of m viscosity modifiers in the formulated oil.
Abstract
Description
Claims
Applications Claiming Priority (2)
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US201762535433P | 2017-07-21 | 2017-07-21 | |
PCT/US2018/041214 WO2019018145A1 (en) | 2017-07-21 | 2018-07-09 | Method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil |
Publications (1)
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EP3655510A1 true EP3655510A1 (en) | 2020-05-27 |
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EP18746440.9A Withdrawn EP3655510A1 (en) | 2017-07-21 | 2018-07-09 | Method for improving deposit control and cleanliness performance in an engine lubricated with a lubricating oil |
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US (1) | US20190031975A1 (en) |
EP (1) | EP3655510A1 (en) |
WO (1) | WO2019018145A1 (en) |
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- 2018-07-09 WO PCT/US2018/041214 patent/WO2019018145A1/en unknown
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US20190031975A1 (en) | 2019-01-31 |
WO2019018145A1 (en) | 2019-01-24 |
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