Lubricating oil composition having resistance to engine deposits - Patents.com

Abstract

The lubricating oil composition comprises greater than 50 weight percent of a base oil of lubricating viscosity and an additive comprising: a) one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, wherein the amount of zinc (Zn) in weight percent provided to the lubricating oil composition by the one or more ZDDPs multiplied by the contribution of the TBN of the one or more dispersants to the total base number (TBN) of the lubricating oil composition has a multiplication index Zn of at least about 0.06. * or b) an additive comprising one or more zinc dialkyldithiophosphate (ZDDP) compounds and one or more dispersants, wherein the amount of phosphorus (P) in weight percent provided to the lubricating oil composition by the one or more ZDDPs multiplied by the contribution of the TBN of the one or more dispersants to the Total Base Number (TBN) of the lubricating oil composition is a multiplication exponent P of at least about 0.051. * and any of the additives, which are TBNDisp.

Description

[Technical Field]

[0001] This disclosure relates to engine lubricating oils with good oxidation resistance and dispersancy properties to reduce engine deposits. In particular, this disclosure relates to lubricating oils and methods for improving the deposit resistance of lubricating oils in engines or other machine parts lubricated with the lubricating oils. The lubricating oils of this disclosure are useful as internal combustion engine oils or in other applications where the lubricating oil is subjected to thermal and oxidative conditions. [Background technology]

[0002] It is desirable for lubricant compositions to exhibit good oxidation resistance and dispersant properties, as well as resistance to soot and sludge, to which lubricant compositions used in internal combustion engines are inevitably exposed during their lifetime. Good dispersant properties can extend the useful life of a lubricant composition, for example, by reducing soot-induced thickening of the lubricant composition or by reducing sludge accumulation in the lubricant composition, which can otherwise rapidly lead to a loss of fuel economy. Typically, the dispersant properties of a lubricant composition are improved by the addition of dispersants. A significant proportion of a lubricant composition may be composed of dispersants, and therefore, they represent a significant cost component of a lubricant composition.

[0003] Oxidation of molecules in lubricating oils can also cause oligomerization, ultimately resulting in a dramatic and irreversible increase in oil viscosity, which can hinder engine operation and reduce efficiency.

[0004] Thus, there is a need in the art for lubricant compositions that have a desirable viscosity profile, including good low temperature viscometrics, and that exhibit good dispersant properties without the need for high dispersant treat rates typically associated with high performance engine oils. Summary of the Invention

[0005] The present disclosure satisfies the above-mentioned need in the art for lubricant compositions having a desirable viscosity profile, including good low temperature viscosity characteristics. The present disclosure also satisfies the need for lubricant compositions that exhibit good dispersant properties without the need for high dispersant treat rates typically associated with high performance engine oils.

[0006] The present invention can be explained by the following text.

[0007] 1. In a first aspect, the present disclosure provides a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition, wherein the additive composition comprises: a lubricating oil composition comprising one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, wherein the lubricating oil composition has a total base number (TBN) of to The amount of zinc (Zn) by weight percent provided to the lubricating oil composition by one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants has a multiplication factor Zn of at least about 0.06. * The lubricating oil composition is TBNDisp.

[0008] 2. Zn * The lubricating oil composition of paragraph 1, wherein the TBNDisp multiplication index may be greater than about 0.07, or from about 0.07 to 0.4, or from about 0.075 to about 0.2.

[0009] 3. Zn * The TBNDisp multiplication index may be at least about 0.06, and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.071 wt. % zinc based on the total weight of the lubricating oil composition, or * 1. The lubricating oil composition of any one of the preceding sentences, wherein the TBNDisp multiplication index is greater than about 0.07 and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.080 wt. % zinc, based on the total weight of the lubricating oil composition.

[0010] 4. Zn * The TBNDisp multiplication index may be at least about 0.06, and the TBN of the lubricating oil composition may be to One or more dispersants have a TBN contribution of at least 0.79 mg KOH / g or Zn * The TBNDisp multiplication index is greater than about 0.07, and the TBN of the lubricating oil composition to The lubricating oil composition of any one of the preceding sentences, wherein the one or more dispersants have a TBN contribution of at least 0.85 mg KOH / g.

[0011] 5. In a second aspect, the present disclosure provides a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition, wherein the additive composition comprises: a lubricating oil composition comprising one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, wherein the lubricating oil composition has a total base number (TBN) of to The amount of phosphorus (P) by weight percent provided to the lubricating oil composition by the one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants is a multiplication index P of at least about 0.051. * The lubricating oil composition is TBNDisp.

[0012] 6.P * 6. The lubricating oil composition of paragraph 5, wherein the TBNDisp multiplication index can be greater than about 0.06 to 0.5, or is from about 0.07 to about 0.25.

[0013] 7.P * The TBNDisp multiplication index may be at least about 0.051, and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.065 wt. % P based on the total weight of the lubricating oil composition, or * 7. The lubricating oil composition of any one of sentences 5-6, wherein the TBNDisp multiplication index is greater than about 0.06 to 0.5, and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.07 wt. % P, based on the total weight of the lubricating oil composition.

[0014] 8.P * The TBNDisp multiplication index may be at least about 0.051, and the TBN of the lubricating oil composition may be toOne or more dispersants have a TBN contribution of at least 0.79 mg KOH / g, or * The TBNDisp multiplication index is greater than about 0.06 to about 0.5, and the TBN of the lubricating oil composition is to 8. The lubricating oil composition of any one of paragraphs 5 to 7, wherein the TBN contribution of the one or more dispersants is at least 0.85 mg KOH / g.

[0015] 9. The lubricating oil composition of any one of sentences 1 to 4, wherein the one or more ZDDP compounds may be present in the lubricating oil composition in an amount of from about 0.01 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 0.5 wt % to about 5 wt %, or from about 0.75 wt % to about 3 wt %, based on the total weight of the lubricating oil composition.

[0016] 10. The lubricating oil composition of any one of sentences 5 to 8, wherein the one or more ZDDP compounds may be present in the lubricating oil composition in an amount of from about 0.01 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 0.5 wt % to about 5 wt %, or from about 0.75 wt % to about 3 wt %, based on the total weight of the lubricating oil composition.

[0017] 11. The lubricating oil composition of any one of sentences 1 to 4 and 9, wherein the amount of one or more dispersants may be greater than about 0.5 wt.%, or may be from about 0.5 wt.% to about 30 wt.%, or from about 0.9 wt.% to about 25 wt.%, or from about 1.0 wt.% to about 15 wt.%, or from about 1.0 wt.% to about 10 wt.%, wherein the amount is based on the total weight of the lubricating oil composition.

[0018] 12. The lubricating oil composition of any one of sentences 5 to 8 and 10, wherein the amount of the one or more dispersants may be greater than about 0.5 wt.%, or may be from about 0.5 wt.% to about 30 wt.%, or from about 0.9 wt.% to about 25 wt.%, or from about 1.0 wt.% to about 15 wt.%, or from about 1.0 wt.% to about 10 wt.%, wherein the amount is based on the total weight of the lubricating oil composition.

[0019] 13. The lubricating oil composition according to any one of sentences 1 to 4, 9 and 11, wherein the one or more ZDDP compounds can be derived from one or more secondary alkyl alcohols having an alkyl group having from 3 to 8 carbon atoms.

[0020] 14. The lubricating oil composition according to any one of paragraphs 5 to 8, 10 and 12, wherein the one or more ZDDP compounds can be derived from one or more secondary alkyl alcohols having an alkyl group having from 3 to 8 carbon atoms.

[0021] 15. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11 and 13, wherein the one or more ZDDP compounds can be derived from a secondary alkyl alcohol selected from the group consisting of isopropyl alcohol, amyl alcohol, and methyl isobutyl carbinol.

[0022] 16. The lubricating oil composition according to any one of sentences 5 to 8, 10, 12 and 14, wherein the one or more ZDDP compounds can be derived from a secondary alkyl alcohol selected from the group consisting of isopropyl alcohol, amyl alcohol, and methyl isobutyl carbinol.

[0023] 17. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13 and 15, wherein the one or more ZDDP compounds may be derived from two or more secondary alkyl alcohols.

[0024] 18. The lubricating oil composition according to any one of paragraphs 5 to 8, 10, 12, 14 and 16, wherein the one or more ZDDP compounds may be derived from two or more secondary alkyl alcohols.

[0025] 19. The lubricating oil composition of any one of sentences 1-4, 9, 11, 13, 15 and 17, wherein the one or more ZDDP compounds may be a mixture of all primary alcohol ZDDP compounds and all secondary alcohol ZDDP compounds.

[0026] 20. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16 and 18, wherein the one or more ZDDP compounds may be a mixture of all primary alcohol ZDDP compounds and all secondary alcohol ZDDP compounds.

[0027] 21. The lubricating oil composition of paragraph 19, wherein the mixture may comprise total primary alcohol ZDDP compounds contributing 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and total secondary alcohol ZDDP compounds contributing 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition, or the mixture may comprise total primary alcohol ZDDP compounds contributing 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and total secondary alcohol ZDDP compounds contributing 300 ppmw to 700 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

[0028] 22. The lubricating oil composition of paragraph 20, wherein the mixture may comprise total primary alcohol ZDDP compounds contributing 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and total secondary alcohol ZDDP compounds contributing 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition, or the mixture may comprise total primary alcohol ZDDP compounds contributing 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and total secondary alcohol ZDDP compounds contributing 300 ppmw to 700 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

[0029] 23. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19 and 21, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols having alkyl groups having 3 to 8 carbon atoms.

[0030] 24. The lubricating oil composition according to any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20 and 22, wherein the one or more ZDDP compounds may be derived from one or more primary alkyl alcohols each having an alkyl group having from 3 to 8 carbon atoms.

[0031] 25. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21 and 23, wherein the alkyl group of the one or more primary alkyl alcohols may have a branch at the beta carbon relative to the hydroxyl group.

[0032] 26. The lubricating oil composition according to any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22 and 24, wherein the alkyl group of the one or more primary alkyl alcohols may have a branch at the beta carbon relative to the hydroxyl group.

[0033] 27. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, and 25, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols selected from the group consisting of n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, 2-butanol, n-phenyl alcohol, hexanol, methyl isobutylcarbinol, isohexanol, n-heptanol, isoheptanol, octanol, amyl alcohol, and 2-ethylhexanol.

[0034] 28. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, and 26, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols selected from the group consisting of n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, 2-butanol, n-phenyl alcohol, hexanol, methyl isobutylcarbinol, isohexanol, n-heptanol, isoheptanol, octanol, amyl alcohol, and 2-ethylhexanol.

[0035] 29. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25 and 27, wherein the one or more ZDDP compounds may be derived from two or more primary alkyl alcohols.

[0036] 30. The lubricating oil composition according to any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 and 28, wherein the one or more ZDDP compounds can be derived from two or more primary alkyl alcohols.

[0037] 31. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, and 29, wherein the one or more ZDDP compounds can be derived from a molar ratio of one or more primary alkyl alcohols to one or more secondary alkyl alcohols of from 100:20 to 50:50.

[0038] 32. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30, wherein the one or more ZDDP compounds can be derived from a molar ratio of one or more primary alkyl alcohols to one or more secondary alkyl alcohols of 100:20 to 50:50.

[0039] 33. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29 and 31, wherein the one or more ZDDP compounds may have a zinc to phosphorus molar ratio of 1.08 to 1.2.

[0040] 34. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, and 32, wherein the one or more ZDDP compounds may have a zinc to phosphorus molar ratio of 1.08 to 1.2.

[0041] 35. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31 and 33, wherein one or more dispersants may be an ashless dispersant.

[0042] 36. The lubricating oil composition according to any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32 and 34, wherein one or more dispersants can be ashless dispersants.

[0043] 37. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, and 35, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 g / mol to about 50,000 g / mol or about 5000 g / mol, or about 500 g / mol to about 3000 g / mol, as measured by GPC.

[0044] 38. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 g / mol to about 50,000 g / mol or about 5000 g / mol, or about 500 g / mol to about 3000 g / mol, as measured by GPC.

[0045] 39. The lubricating oil composition according to any one of sentences 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35 and 37, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyamine or a hydroxylamine.

[0046] 40. The lubricating oil composition according to any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36 and 38, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyamine or a hydroxylamine.

[0047] 41. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37 and 39, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), higher polyethyleneamine (PEA) homologs and mixtures thereof, or the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylamine hexamine (PEHA), or the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from PEA used alone or in combination with TEPA.

[0048] 42. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, and 40, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), higher polyethyleneamine (PEA) homologs, and mixtures thereof, or the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylamine hexamine (PEHA), or the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from PEA used alone or in combination with TEPA.

[0049] 43. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, and 41, wherein the one or more dispersants may have 0.1 wt. % to 5 wt. % nitrogen, or 0.25 wt. % to 3 wt. % nitrogen, or 0.5 wt. % to 2 wt. % nitrogen, based on the total weight of the one or more dispersants.

[0050] 44. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, and 42, wherein the one or more dispersants may have 0.1 wt. % to 5 wt. % nitrogen, or 0.25 wt. % to 3 wt. % nitrogen, or 0.5 wt. % to 2 wt. % nitrogen, based on the total weight of the one or more dispersants.

[0051] 45. The lubricating oil composition of any one of sentences 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, and 43, wherein the one or more dispersants may comprise at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), the PIBSA having an average of between about 1.0 and about 2.0 succinic moieties per polyisobutylene (PIB) polymer, or between about 1.1 and about 1.8 succinic moieties per PIB polymer.

[0052] 46. ​​The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, and 44, wherein the one or more dispersants may comprise at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), the PIBSA having an average of between about 1.0 and about 2.0 succinic moieties per polyisobutylene (PIB) polymer, or between about 1.1 and about 1.8 succinic moieties per PIB polymer.

[0053] 47. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, and 45, wherein each of the one or more dispersants may have a TBN of from about 10 mg KOH / g to about 65 mg KOH / g on an oil-free basis, as measured by the method of ASTM D2896.

[0054] 48. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, and 46, wherein each of the one or more dispersants may have a TBN of from about 10 mg KOH / g to about 65 mg KOH / g on an oil-free basis, as measured by the method of ASTM D2896.

[0055] 49. TBN of lubricating oil composition to 48. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, and 47, wherein the total dispersant TBN contribution may be at least 0.79 mg KOH / g, or at least 0.85 mg KOH / g, or from 0.85 mg KOH / g to 5 mg KOH / g, or from 0.9 mg KOH / g to 2.5 mg KOH / g.

[0056] 50. TBN of lubricating oil composition to 49. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, and 48, wherein the total dispersant TBN contribution may be at least 0.79 mg KOH / g, or is at least 0.85 mg KOH / g, or is from 0.85 mg KOH / g to 5 mg KOH / g, or is from 0.9 mg KOH / g to 2.5 mg KOH / g.

[0057] 51. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, and 49, wherein the one or more dispersants may comprise at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, phosphorus compounds, and mixtures thereof, or wherein the one or more dispersants comprise at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0058] 52. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, and 50, wherein the one or more dispersants may comprise at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, phosphorus compounds, and mixtures thereof, or wherein the one or more dispersants comprise at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0059] 53. The lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49 and 51, wherein the one or more dispersants can be a mixture of at least one dispersant that has been post-treated and at least one dispersant that has not been post-treated.

[0060] 54. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, and 52, wherein the one or more dispersants can be a mixture of at least one dispersant that has been post-treated and at least one dispersant that has not been post-treated.

[0061] 55. The lubricating oil composition of any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, and 53, wherein the amount of the one or more dispersants is from about 0.1 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 8 wt. %, or from about 1 wt. % to about 10 wt. %, or from about 1 wt. % to about 8 wt. %, or from about 1 wt. % to about 7 wt. %, based on the total weight of the lubricating oil composition.

[0062] 56. The lubricating oil composition of any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, and 54, wherein the amount of the one or more dispersants can be from about 0.1 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 8 wt. %, or from about 1 wt. % to about 10 wt. %, or from about 1 wt. % to about 8 wt. %, or from about 1 wt. % to about 7 wt. %, based on the total weight of the lubricating oil composition.

[0063] 57. The lubricating oil composition of any one of sentences 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, and 55, which may further comprise at least one additive selected from the group consisting of dispersants, antioxidants, antiwear agents, antifoam agents, molybdenum-containing compounds, titanium-containing compounds, phosphorus-containing compounds, pour point depressants, and diluent oils.

[0064] 58. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, and 56, which may further comprise at least one additive selected from the group consisting of dispersants, antioxidants, antiwear agents, antifoam agents, molybdenum-containing compounds, titanium-containing compounds, phosphorus-containing compounds, pour point depressants, and diluent oils.

[0065] 59. The lubricating oil composition of any one of sentences 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, and 57, wherein the lubricating oil composition is capable of providing an average engine sludge test (ASTM D8256) result of 7.01 minutes or more, or 7.05 minutes or more, or from 7.05 minutes to about 15 minutes.

[0066] 60. The lubricating oil composition of any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, and 58, wherein the lubricating oil composition is capable of providing an average engine sludge test (ASTM D8256) result of 7.01 minutes or more, or 7.05 minutes or more, or from 7.05 minutes to about 15 minutes.

[0067] 61. A method for reducing engine sludge in an internal combustion engine, the method comprising adding to the engine a lubricating oil composition described in any one of sentences 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, and 59, and operating the engine.

[0068] 62. A method for reducing engine sludge in an internal combustion engine, comprising adding to the engine a lubricating oil composition according to any one of sentences 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, and 60, and operating the engine.

[0069] 63. A method for improving fuel economy and / or piston cleanliness performance of an engine and / or vehicle, comprising providing to the engine and / or vehicle a lubricating oil composition according to any one of sentences 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57 and 59.

[0070] 64. A method for improving fuel economy and / or piston cleanliness performance of an engine and / or vehicle, comprising providing to the engine and / or vehicle a lubricating oil composition according to any one of sentences 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 and 60.

[0071] The following definitions are provided to clarify the meaning of certain terms used herein.

[0072] The terms "oil composition," "lubrication composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "lubricating composition," "fully formulated lubricant composition," "lubricant," "crankcase oil," "crankcase lubricant," "engine oil," "engine lubricant," "motor oil," and "motor lubricant" are considered to be synonymous and fully interchangeable terms that refer to a finished lubricant product that includes a major amount of a base oil plus a minor amount of an additive composition.

[0073] As used herein, the terms "additive package," "additive concentrate," "additive composition," "engine oil additive package," "engine oil additive concentrate," "crankcase additive package," "crankcase additive concentrate," "motor oil additive package," and "motor oil concentrate" are considered synonymous and fully interchangeable terms that refer to that portion of a lubricating oil composition that excludes a major amount of a base oil stock blend. The additive package may or may not include a viscosity index improver or a pour point depressant.

[0074] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, salicylates, and / or phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have conversion levels greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts, the MR is greater than 1. These are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, and / or phenols.

[0075] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, where the substituted hydrocarbon substituents contain one or more of halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbyl group.

[0076] As used herein, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule by carbon atoms at two locations and has a predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, including halo, alkyl, aryl, alkylaryl, arylalkyl, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbylene group.

[0077] As used herein, the term "weight percent" means the percentage that the recited component represents relative to the weight of the entire composition, unless expressly stated otherwise.

[0078] The terms "soluble," "oil-soluble," or "dispersible" as used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or capable of being suspended in oil in any proportion. However, the terms do mean that they are, for example, soluble, suspendable, dissolvable, or stably dispersible in oil to a sufficient degree to exert their intended effect in the environment in which the oil is used. Furthermore, if desired, the incorporation of other additives may also allow for the incorporation of higher levels of the specific additive.

[0079] As employed herein, the term "TBN" is used to indicate the total base number in mg KOH / g as measured by the methods of ASTM D2896 or ASTM D4739 or DIN 51639-1.

[0080] The term "alkyl" as used herein refers to straight, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms.

[0081] The term "alkenyl," as used herein, refers to straight, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms.

[0082] The term "aryl" as used herein refers to mono- and polycyclic aromatic compounds that can include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0083] The lubricants, combinations of components, or individual components herein may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy-duty diesel, passenger car, light-duty diesel, medium-speed diesel, or marine engines. The internal combustion engine may be a diesel-fueled engine, a gasoline-fueled engine, a natural gas-fueled engine, a biofueled engine, a mixed diesel / biofuel-fueled engine, a mixed gasoline / biofuel-fueled engine, an alcohol-fueled engine, a mixed gasoline / alcohol-fueled engine, a compressed natural gas (CNG)-fueled engine, or a mixture thereof. The diesel engine may be a compression-ignition engine. The gasoline engine may be a spark-ignition engine. The internal combustion engine may also be used in combination with electric or battery power sources. Engines configured in this manner are typically known as hybrid engines. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine vessels), aviation piston engines, light-duty diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks.

[0084] An internal combustion engine may include one or more components of aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and / or mixtures thereof. The components may be coated, for example, with a diamond-like carbon coating, a lubricating coating, a phosphorus-containing coating, a molybdenum-containing coating, a graphite coating, a nanoparticle-containing coating, and / or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is synonymous with "aluminum composite" and is intended to describe a component or surface that includes aluminum and another component that mixes or reacts at a microscopic or near-microscopic level, regardless of its detailed structure. This includes conventional alloys with metals other than aluminum, as well as composite or alloy-like structures with non-metallic elements or compounds, such as ceramic-like materials.

[0085] The lubricating oil composition for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt. % or less, or about 0.8 wt. % or less, or about 0.5 wt. % or less, or about 0.3 wt. % or less, or about 0.2 wt. % or less. In one embodiment, the sulfur content may range from about 0.001 wt. % to about 0.5 wt. %, or from about 0.01 wt. % to about 0.3 wt. %. The phosphorus content may be about 0.2 wt. % or less, or about 0.1 wt. % or less, or about 0.06 wt. % or less, or about 0.2 wt. In one embodiment, the phosphorus content may be about 500 ppmw to about 1250 ppmw, or about 600 ppmw to about 1200 ppmw. The total sulfated ash content may be about 2% by weight or less, or about 1.5% by weight or less, or about 1.1% by weight or less, or about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less. In one embodiment, the sulfated ash content may be about 0.05% by weight to about 0.9% by weight, or 0.1% by weight or about 0.2% by weight to about 0.45% by weight. In another embodiment, the sulfur content may be about 0.4% by weight or less, the phosphorus content may be about 0.12% by weight or less, and the sulfated ash content may be about 1% by weight or less. In yet another embodiment, the sulfur content may be about 0.3% by weight or less, the phosphorus content may be about 0.11% by weight or less, and the sulfated ash content may be about 0.8% by weight or less.

[0086] In one embodiment, the lubricating oil composition is an engine oil, and the lubricating oil composition may have (i) a sulfur content of less than or equal to about 0.5 wt. %, (ii) a phosphorus content of less than or equal to about 0.1 wt. %, and (iii) a sulfated ash content of less than or equal to about 1.5 wt. %.

[0087] In one embodiment, the lubricating oil composition is suitable for a two-stroke or four-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel combustion engine is a two-stroke engine. In some embodiments, the lubricating oil composition is not suitable for a two-stroke or four-stroke marine diesel internal combustion engine for one or more reasons, including, but not limited to, the high sulfur content of fuels used to power marine engines and the high TBN required for engine oils suitable for marine use (e.g., greater than about 40 TBN for engine oils suitable for marine use).

[0088] In some embodiments, the lubricating oil compositions are suitable for use in engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuels contain about 15 ppmw sulfur (or about 0.0015% sulfur).

[0089] Low-speed diesels typically refer to marine engines, medium-speed diesels typically refer to locomotives, and high-speed diesels typically refer to highway vehicles. A lubricating oil composition may be suitable for only one or all of these types.

[0090] Additionally, the lubricants herein may meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-5+, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, SN PLUS, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, A7 / B7, C1, C2, C3, C4, C5, C6 E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or Dexos1™, Dexos2™, MB-Approval. 229.1, 229.3, 229.5, 22.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.The present invention may be suitable for meeting original equipment manufacturer specifications, such as STJLR.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specifications not listed herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppmw or less, or 900 ppmw or less, or 800 ppmw or less.

[0091] Other hardware may not be suitable for use with the disclosed lubricants. "Functional fluid" is a term that encompasses a variety of fluids, including, but not limited to, tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines and compressors, some industrial fluids, and fluids associated with power transmission components. It should be noted that within each of these fluids, such as automatic transmission fluids, there are a variety of different types of fluids for different transmissions with different designs that require fluids with significantly different functional properties. This is in contrast to the term "lubricating fluid," which is not used to generate or transmit power.

[0092] For example, with respect to tractor hydraulic fluids, these fluids are general-purpose fluids used for all lubrication applications in tractors except for lubricating the engine, which may include lubricating the gearbox, power take-offs and clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

[0093] When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction to allow the clutch plates to transmit power. However, the coefficient of friction of the fluid tends to decrease with temperature as the fluid heats up during operation. It is important for a tractor's hydraulic fluid or automatic transmission fluid to maintain a high coefficient of friction at high temperatures, otherwise the brake system or automatic transmission may fail. This is not the function of engine oil.

[0094] Tractor fluids, such as Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO), may combine engine oil performance with transmission, differential, final drive planetary gear, wet brake, and hydraulic performance. Many of the additives used to formulate UTTO or STUO fluids are functionally similar but can have deleterious effects if not properly incorporated. For example, some anti-wear and extreme pressure additives used in engine oils can be highly corrosive to copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake squeal may lack the thermal stability necessary for engine oil performance. Each of these fluids is designed to meet specific, stringent manufacturer requirements, whether for functionality, tractor, or lubricity.

[0095] The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. The present disclosure provides novel lubricating oil blends formulated for use as 2T and / or 4T motorcycle crankcase lubricants. Embodiments of the present disclosure may provide lubricating oils that are suitable for crankcase applications and have improved air entrainment, alcohol fuel compatibility, antioxidant properties, antiwear performance, biofuel compatibility, foam reduction properties, friction reduction, fuel economy, pre-ignition prevention, rust prevention, sludge and / or soot dispersancy, piston cleanliness, deposit formation, and water resistance properties.

[0096] The engine oils of the present disclosure may be formulated by adding one or more additives to a suitable base oil formulation, as described in detail below. The additives may be combined with the base oil in the form of an additive package (or concentrate), or alternatively, may be combined individually with the base oil (or a mixture of both). The fully formulated engine oil may exhibit improved performance characteristics based on the additives added and their respective proportions.

[0097] Further details and advantages of the present disclosure will be set forth in part in the description which follows and / or may be learned by practice of the present disclosure. The details and advantages of the present disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure as claimed. [Brief explanation of the drawings]

[0098] [Figure 1] 1 is a graph of the amount of zinc (Zn) in weight percent provided to a lubricating oil composition by one or more ZDDPs multiplied by the total base number (TBN) contribution of one or more dispersants to the lubricating oil composition's TBN versus average engine sludge. [Figure 2]1 is a graph of the amount of phosphorus (P) in weight percent provided to a lubricating oil composition by one or more ZDDPs multiplied by the total base number (TBN) contribution of one or more dispersants to the lubricating oil composition's TBN versus average engine sludge. DETAILED DESCRIPTION OF THE INVENTION

[0099] This disclosure relates to lubricating oil compositions having reduced engine deposits. In particular, this disclosure relates to lubricating oil compositions and methods for improving the deposit resistance of lubricants in engines or other machine parts lubricated with the lubricants. The lubricants of this disclosure are useful as passenger vehicle engine oil (PVEO) products, commercial vehicle engine oil (CVEO) products, or other applications where the lubricant is subjected to thermal and oxidative conditions.

[0100] In one embodiment, the lubricating oil composition of the present invention comprises greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, and the total base number (TBN) of the lubricating oil composition is to The amount of zinc (Zn) by weight percent provided to the lubricating oil composition by one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants has a multiplication factor Zn of at least about 0.06. * TBNDisp.

[0101] In another embodiment, the lubricating oil composition of the present invention comprises greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, wherein the lubricating oil composition has a total base number (TBN) of greater than 50 wt. % of the base oil of lubricating viscosity and an additive composition comprising one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants. to The amount of phosphorus (P) by weight percent provided to the lubricating oil composition by the one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants is a multiplication index P of at least about 0.051. *TBNDisp.

[0102] ZDDP has antioxidant and antiwear functions. Without being bound by theory, it is believed that ZDDP acts as an antioxidant to minimize the formation of deposit precursors such as hydroperoxides and radicals. These species are reactive and attack the hydrocarbon base oil and additives that make up the lubricant, forming sludge, resins, varnish, and hard deposits. The dispersant works in concert with ZDDP by keeping these entities suspended in the bulk lubricant. This not only provides improved deposit control, but also minimizes the abrasive wear and viscosity increase associated with particulates.

[0103] As discussed in detail below, the lubricating oil compositions were tested according to the Sequence VH Engine Test. The Sequence VH Test (ASTM D8256) is a test method used to evaluate engine deposit control by automotive engine oils under operating conditions purposefully selected to accelerate deposit formation. The engine is a gasoline-fueled, spark-ignition engine operated under low-temperature, light-load conditions. One of the measurements included in the Sequence VH Test is a measurement of average engine sludge. Engine cleanliness is measured by sludge merit, with higher scores indicating cleaner engines.

[0104] In some embodiments, the engine oil has at least about 0.06% Zn * When combined with an additive composition having the TBNDisp Multiplication Index characteristic, and one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.071 wt. % zinc, based on the total weight of the lubricating oil composition, there is improved engine deposit resistance relative to engine oil formulations lacking that characteristic.

[0105] In another embodiment, the engine oil * The TBNDisp multiplication index of the lubricating oil composition is at least about 0.06, and toWhen combined with an additive composition characterized by one or more dispersants having a TBN contribution of at least 0.79 mg KOH / g, there is improved engine deposit resistance relative to engine oil formulations lacking that characteristic.

[0106] In yet another embodiment, the engine oil has a P * When combined with an additive composition having the TBNDisp Multiplication Index characteristic, and one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.065 wt. % P, based on the total weight of the lubricating oil composition, there is improved resistance to engine deposits relative to engine oil formulations lacking that characteristic.

[0107] In a further embodiment, the engine oil comprises P * The TBNDisp multiplication index of the lubricating oil composition is at least about 0.051, and to When combined with an additive composition characterized by one or more dispersants having a TBN contribution of at least 0.79 mg KOH / g, there is improved engine deposit resistance relative to engine oil formulations lacking that characteristic.

[0108] base oil The base oil used in the lubricating oil compositions herein may be selected from any of the base oils in Groups I to V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are set forth in Table 1 below.

[0109] [Table 1]

[0110] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0111] The base oil used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0112] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been treated with one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0113] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained using the same or similar processes as refined oils. Often, these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0114] Mineral oils may include oils obtained by drilling, or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0115] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0116] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils can be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0117] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0118] The amount of oil of lubricating viscosity present may be the remaining amount remaining after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treatment additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0119] Dispersants The lubricating oil composition further contains one or more dispersants. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to being mixed into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 g / mol to about 50,000 g / mol or about 5,000 g / mol, or from about 500 g / mol to about 3,000 g / mol, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0120] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA). In some embodiments, the amine is PEA, used alone or in combination with TEPA.

[0121] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures, although they contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine). Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) of total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0122] In some approaches, suitable polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0123] Typically, PAM has 8.7 to 8.9 milliequivalents of primary amine per gram (115 to 112 grams of equivalents per equivalent of primary amine) and a total nitrogen content of about 33% to 34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogens and more extensive branching, may produce dispersants with improved dispersancy.

[0124] In some embodiments, the one or more dispersants have from 0.1% to 5% by weight nitrogen, or from 0.25% to 3% by weight nitrogen, or from 0.5% to 2% by weight nitrogen, based on the total weight of the one or more dispersants.

[0125] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight ranging from about 350 g / mol to about 50,000 g / mol or about 5,000 g / mol, or from about 500 g / mol to about 3,000 g / mol, as measured by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0126] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight, as measured by GPC, ranging from about 800 g / mol to about 5000 g / mol is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0127] HR-PIB having a number average molecular weight ranging from about 900 g / mol to about 3000 g / mol, as measured by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0128] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of between about 1.0 and about 2.0 succinic moieties per polymer, or between about 1.1 and about 1.8 succinic moieties per PIB polymer.

[0129] The percent active ingredient of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0130] Polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0131] Unless otherwise specified, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 g / mol to about 18,000 g / mol) as calibration standards.

[0132] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In some embodiments, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0133] The TBN of suitable dispersants may be from about 10 mg / KOH / g to about 65 mg / KOH / g on an oil-free basis, when measured on dispersant samples containing about 50% diluent oil, which corresponds to a TBN of from about 5 mg / KOH / g to about 30 mg / KOH / g. TBN is measured by the method of ASTM D2896.

[0134] TBN of the lubricating oil composition to The TBN contribution of the total dispersant is at least 0.79 mg KOH / g, or at least 0.85 mg KOH / g, or from 0.85 mg KOH / g to 5 mg KOH / g, or from 0.9 mg KOH / g to 2.5 mg KOH / g. TBN is measured by method D2896.

[0135] A suitable type of nitrogen-containing dispersant can be derived from an olefin copolymer (OCP), more specifically, an ethylene-propylene dispersant that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with the functionalized OCP is described in U.S. Patent Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383, and / or is commercially available.

[0136] Alternatively, the hydrocarbyl portion of the hydrocarbyl-dicarboxylic acid or anhydride of component A) can be derived from an ethylene-alphaolefin copolymer. These copolymers contain a plurality of ethylene units and a plurality of one or more C3-C6 10 Contains alpha-olefin units. C3-C 10 The alpha-olefin units may include propylene units.

[0137] One type of suitable dispersant can be a Mannich base. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0138] A suitable class of dispersants may also be high molecular weight esters or half ester amides.

[0139] Suitable dispersants can also be post-treated by conventional methods with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. Preferably, the dispersant is post-treated with boron and maleic anhydride. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entireties.

[0140] The one or more dispersants can be a mixture of at least one dispersant that has been post-treated and at least one dispersant that has not been post-treated. The weight ratio of the post-treated dispersant to the non-post-treated dispersant can be from about 5:1 to about 1:15, or from about 4:1 to about 1:10.

[0141] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with: inorganic phosphoric acid or anhydride (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organophosphorus compounds (e.g., U.S. Pat. No. 3,502,677); Phosphorus pentasulfide; boron compounds, such as those already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386); epoxide polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. Nos. 3,312,619, 3,865,813, and British Pat. No. 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Pat. No. 2,140,811); Alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); Diketene (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); Alkanesultones (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); Sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); Cyclic lactones (e.g., U.S. Patent Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275, and 4,971,711); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170); Nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Pat. No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or ditholactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390; 4,646,860, and 4,670,170); Nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Pat. No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); Hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318; 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); A combination of phosphorus pentasulfide and polyalkylenepolyamines (e.g., U.S. Pat. No. 3,185,647); Combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098); A combination of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); Combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, and 5,039,307); Combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740); A combination of a hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Pat. No. 4,554,086); A combination of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); Combinations of hydroxyaliphatic carboxylic acids followed by aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); A combination of formaldehyde and phenol followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); a combination of a hydroxyaliphatic carboxylic acid or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); Combinations of inorganic acids or anhydrides of phosphorus or their partial or total sulfur analogs and boron compounds (e.g., U.S. Pat. No. 4,857,214); A combination of an organic diacid, followed by an unsaturated fatty acid, and then a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); A combination of an aldehyde and a triazole followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); Combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711), which are incorporated herein by reference in their entireties.

[0142] One or more dispersants may be used in an amount sufficient to provide up to about 20 wt. %, based on the final weight of the lubricating oil composition. Alternative amounts of one or more dispersants that may be used may be from about 0.1 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 8 wt. %, or from about 1 wt. % to about 10 wt. %, or from about 1 wt. % to about 8 wt. %, or from about 1 wt. % to about 7 wt. %, based on the total weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0143] Zinc dialkyldithiophosphate compounds The lubricating oil compositions of the present disclosure for use in internal combustion engines to reduce engine sludge contain an amount of one or more zinc dialkyldithiophosphates (ZDDP compounds). The one or more ZDDP compounds can also help improve the friction and wear properties of the lubricating oil composition.

[0144] The one or more ZDDP compounds are present in the lubricating oil composition in an amount of from about 0.01 wt % to about 15 wt %, or from about 0.01 wt % to about 10 wt %, or from about 0.05 wt % to about 5 wt %, or from about 0.1 wt % to about 3 wt %, or from about 0.1 wt % to about 1.5 wt %, based on the total weight of the lubricating oil composition.

[0145] The one or more ZDDP compounds may include ZDDPs derived from primary alkyl alcohols, secondary alkyl alcohols, or combinations of primary and secondary alkyl alcohols. The primary and secondary alkyl alcohols used to prepare the one or more ZDDP compounds may have alkyl groups containing 1 to 20 carbon atoms, or about 1 to 18 carbon atoms, or about 1 to about 16 carbon atoms, or 2 to 12 carbon atoms, or about 3 to about 8 carbon atoms. Preferably, the primary alkyl alcohol has a branch at the beta carbon relative to the hydroxyl group.

[0146] For example, an alcohol with a branch at the beta (β) carbon will have a branch at the second carbon counting from the oxygen atom of the hydroxyl group.

[0147] [ka]

[0148] Suitable examples of primary and secondary alkyl alcohols for use in preparing one or more ZDDP compounds may be selected from n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanol, isobutyl alcohol, n-pentyl alcohol, amyl alcohol, hexanol, methyl isobutylcarbinol, isohexanol, n-heptanol, isoheptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, and 2-ethylhexanol.

[0149] The molar ratio of primary alkyl alcohol to secondary alkyl alcohol used to make the one or more ZDDP compounds in the lubricating oil composition can be from about 1:5 to 2:1. The one or more ZDDP compounds can have a P:Zn molar ratio of from about 1.08 to 1.3, or from about 1.08 to 1.2, or from about 1.09 to about 1.15. In some embodiments, the one or more ZDDP compounds can be overbased with zinc oxide.

[0150] In some embodiments, the additive composition may include at least two different zinc dialkyldithiophosphate compounds. The two alkyl groups on the zinc dialkyldithiophosphate compounds may be the same or different.

[0151] In some embodiments, 100 mole percent of the alkyl groups on one or more of the ZDDP compounds may be derived from one or more primary alcohol groups. In some embodiments, 100 mole percent of the alkyl groups on one or more of the ZDDP compounds may be derived from one or more secondary alcohol groups. In some embodiments, a mixture of one or more all-primary alcohol ZDDP compounds and one or more all-secondary alcohol ZDDP compounds is provided. In some embodiments, the mixture includes total secondary alcohol ZDDP compounds contributing 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and total secondary alcohol ZDDP compounds contributing 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition, or the mixture includes one or more total primary alcohol ZDDP compounds contributing 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and one or more total secondary alcohol ZDDP compounds contributing 300 ppmw to 700 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

[0152] The alcohol suitable for producing one or more ZDDP compounds can be a primary alkyl alcohol, a secondary alkyl alcohol, or a mixture of primary and secondary alkyl alcohols. In one embodiment, the additive package includes one ZDDP compound derived from an alcohol containing a primary alkyl group and another ZDDP compound derived from an alcohol containing a secondary alkyl group. In another embodiment, the ZDDP compound is derived from at least two secondary alcohols. The alcohols may be branched, cyclic, or linear.

[0153] The one or more ZDDP compounds may be an oil-soluble salt of a dihydrocarbyl dithiophosphate, having the following formula:

[0154] [ka]

[0155] wherein R5 and R6 may be the same or different alkyl groups containing 1 to 20 carbon atoms, or about 1 to 18 carbon atoms, or about 1 to about 16 carbon atoms, or 2 to 12 carbon atoms, or about 3 to about 8 carbon atoms, and including moieties such as alkyl and cycloalkyl moieties. Thus, the moieties can be, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, 4-methyl-pentyl, n-octyl, decyl, dodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylhexyl, nonadecyl, eicosyl, 2-ethylhexyl, cyclohexyl, or methylcyclopentyl.

[0156] The average number of total carbon atoms per mole of phosphorus in a ZDDP compound may be calculated by summing the carbon atoms in the four alkyl groups R5 and R6 provided to the ZDDP compound by the alcohol used to make the ZDDP compound and dividing by 2. For example, in a single ZDDP compound, if R5 is a C3-alkyl group and R6 is a C6 alkyl group, the total number of carbon atoms is 3 + 3 + 6 + 6 = 18. Dividing this by the 2 moles of phosphorus per mole of ZDDP gives an average total of 9 carbon atoms per mole of phosphorus.

[0157] The average total number of carbon atoms per mole of phosphorus (ATCP) for a composition containing one or more ZDDP compounds can be calculated from the alcohol used to produce the ZDDP compound according to the following formula: ATCP=2 * [(mol% of Alc1 * (number of C atoms in alc1) + (mol% of alc2 * (number of C atoms in alc2) + (mol% of alc3 * number of C atoms in alc3) + ... etc.] where alc1, alc2, and alc3 each represent a different alcohol used to make the ZDDP compound, and mole % is the mole percentage of each alcohol present in the reaction mixture used to make the ZDDP compound. "And so on" indicates that if more than three alcohols are used to make the ZDDP compound, the formula can be expanded to include each alcohol present in the reaction mixture.

[0158] The average total number of carbon atoms from both R5 and R6 of the ZDDP is greater than 2 carbon atoms per mole of phosphorus, and in one embodiment in the range of greater than 4 to 40 carbon atoms, or greater than 6 to about 20 carbon atoms, and in one embodiment in the range of greater than 6 to about 16 carbon atoms, and in one embodiment in the range of about 6 to about 15 carbon atoms, and in one embodiment in the range of about 9 to about 15 carbon atoms, and in one embodiment about 12 carbon atoms per mole of phosphorus.

[0159] The zinc dialkyldithiophosphate compounds may be prepared according to known techniques by first forming a dialkyldithiophosphoric acid (DDPA), usually by reaction with one or more alcohols, and then neutralizing the formed DDPA with a zinc compound. Any basic or neutral zinc compound may be used to make the compound, although oxides, hydroxides, and carbonates are most commonly used. The zinc dialkyldithiophosphates of component (i) may be made by processes such as those generally described in U.S. Pat. No. 7,368,596.

[0160] In some embodiments, at least one ZDDP compound may be present in the lubricating oil in an amount sufficient to provide from about 100 to about 1500 ppmw of phosphorus, or from about 100 ppmw to about 1000 ppmw of phosphorus, or from about 200 ppmw to about 1300 ppmw of phosphorus, or from about 300 ppmw to about 1200 ppmw of phosphorus, or from about 550 ppmw to about 1200 ppmw of phosphorus, based on the total weight of the lubricating oil composition.

[0161] In some embodiments, at least one ZDDP compound may be present in the lubricating oil in an amount sufficient to provide from about 10 ppmw zinc to about 1500 ppmw zinc, or from about 100 ppmw zinc to about 1300 ppmw zinc, or from about 600 ppmw zinc to about 1200 ppmw zinc, based on the total weight of the lubricating oil composition.

[0162] The use of one or more ZDDP compounds derived from a molar ratio of primary alkyl alcohol to secondary alkyl alcohol of about 100:0 to about 0:100 unexpectedly provides increased viscosity control across a wide variety of ZDDP compounds compared to the same lubricating oil composition, except that it does not contain a ZDDP compound. Specifically, the use of one or more ZDDP compounds derived from 100 mole percent of one or more secondary alkyl alcohols and / or one or more ZDDP compounds derived from 100 mole percent of one or more primary alkyl alcohols to improve viscosity control unexpectedly increased resistance to sludge.

[0163] Additionally, the use of one or more ZDDP compounds derived from all secondary alkyl alcohols to one or more ZDDP compounds derived from all primary alkyl alcohols in a molar ratio ranging from 100:0 to 0.2:1, or from 10:1 to 0.4:1, or from 6:1 to 0.75:1 provides improved friction and / or wear results and / or viscosity control across a wide variety of ZDDP compounds compared to lubricating oil compositions other than those lacking the ZDDP compound.

[0164] The present invention may include an overbased ZDDP, which is a basic ZDDP. The term "basic ZDDP," or equivalent expressions, is used herein to describe a zinc salt in which the metal substituent is present in a stoichiometrically greater amount than the phosphate radical. For example, a normal or neutral zinc phosphorodithioate has two equivalents (i.e., one mole) of zinc per two equivalents (i.e., two moles) of phosphorodithioic acid, while a basic zinc diorganophosphorodithioate has more than two equivalents of zinc per two equivalents of phosphorodithioic acid.

[0165] For example, overbasing can be carried out using a basic zinc compound such as zinc oxide. The amount of basic base compound required to provide the desired overbasing is not critical. The essential factor is that sufficient zinc compound be present in the reaction mixture for the overbasing reaction. While not absolutely necessary, it has been found that the reaction proceeds in a more satisfactory manner when a slight excess of zinc compound is used over the amount required for the reaction. This excess should be kept to a minimum level relative to the need to remove large amounts of solids from the final product. As a general statement, the excess zinc compound should not exceed 10-15% by weight.

[0166] friction modifiers The lubricating oil compositions herein may optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonic acids, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil and other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0167] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, a di-ester, or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0168] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0169] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0170] The amines and amides may be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0171] Friction modifiers may optionally be present in ranges such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0172] antioxidants The lubricating oil compositions herein may also optionally contain one or more antioxidants in addition to one or more ZDDP compounds. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0173] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox® L-135 available from BASF, or an adduct derived from 2,6-di-tert-butylphenol and an alkyl acrylate. The alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox™ 4716 available from Albemarle Corporation.

[0174] Useful antioxidants may include diarylamines and high molecular weight phenols. In some embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In some embodiments, the antioxidant may be a mixture of about 0.3 wt. % to about 1.5 wt. % diarylamines and about 0.4 wt. % to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0175] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene, such as 1,3-butadiene, and an unsaturated ester, such as butyl acrylate.

[0176] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with an olefin, such as an α-olefin.

[0177] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the ratio of phenol to amine to molybdenum-containing is (0-2):(0-2):(0-1).

[0178] The one or more antioxidants may be present in the range of about 0% to about 20%, or about 0.1% to about 10%, or about 1% to about 5% by weight of the lubricating oil composition.

[0179] Anti-wear agent The lubricating oil compositions herein may also optionally contain one or more antiwear agents in addition to one or more ZDDP compounds. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0180] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrate.

[0181] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0182] Boron-containing compounds The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.

[0183] Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057.

[0184] When present, the boron-containing compound may be used in an amount sufficient to provide up to about 8 wt %, from about 0.01 wt % to about 7 wt %, from about 0.05 wt % to about 5 wt %, or from about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0185] Detergent The lubricating oil composition may contain one or more detergents. The one or more detergents may be neutral, underbased, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein.

[0186] One or more detergents may be formed from a detergent substrate salified with an alkali metal or another alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free.

[0187] Suitable detergents may include salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0188] One or more detergents may be overbased detergents. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted carboxylic acid, or an aliphatic-substituted phenol.

[0189] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0190] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or greater, or, as a further example, about 225 mg KOH / gram or greater, or about 250 mg KOH / gram or greater, or about 300 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater.

[0191] Preferably, the one or more detergents comprise an overbased calcium-containing detergent. Examples of suitable overbased calcium-containing detergents include, but are not limited to, overbased calcium phenate, overbased sulfur-containing calcium phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium monothiophosphate and / or dithiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bonded alkylphenol compound, and overbased calcium methylene-bridged phenol. Preferably, the overbased calcium-containing detergent is an overbased calcium sulfonate detergent.

[0192] Examples of other suitable overbased detergents include, but are not limited to, overbased magnesium phenate, overbased sulfur-containing magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-linked alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0193] Overbased detergents may have a metal to substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater.

[0194] The one or more detergents may be low-based / neutral detergents having a TBN of up to 175 mg KOH / g or up to 150 mg KOH / g. The low-based / neutral detergent may be formed from a detergent substrate salified with an alkali metal or another alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. The low-based / neutral detergent may be selected from a sulfonate, phenate, or salicylate detergent. In some embodiments, the low-based / neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low-based / neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent. In embodiments, the one or more detergents comprise a mixture of one or more low-based / neutral calcium-containing detergents and one or more overbased calcium-containing detergents.

[0195] The one or more detergents may include overbased calcium-containing detergents and low-based / neutral detergents that are salts of alkali metals or alkaline earth metals other than calcium.

[0196] The amount of calcium provided by the one or more calcium-containing detergents is greater than about 0.01 wt. %, or greater than about 0.02 wt. %, or up to about 0.25 wt. %, or from about 0.010 wt. % to about 0.25 wt. %, or from about 0.02 wt. % to about 0.20 wt. %, or from about 0.02 wt. % to about 0.15 wt. %, where the amount is based on the total weight of the lubricating oil composition.

[0197] The low-based / neutral detergent may provide calcium in an amount that constitutes at least 0.001 wt. % of the calcium provided by the total detergents in the lubricating oil composition. In some embodiments, the low-based / neutral detergent may provide calcium in an amount that constitutes at least 0.003 wt. %, or between 0.003 wt. % and 0.05 wt. % of the calcium provided by the total detergents in the lubricating oil composition.

[0198] In certain embodiments, the one or more low-based / neutral detergents provide the lubricating oil composition with from about 1 ppmw to about 400 ppmw of calcium by weight, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low-based / neutral calcium-containing detergents provide the lubricating oil composition with from 1 ppmw to 350 ppmw of calcium by weight, based on the total weight of the lubricating oil composition.

[0199] In some embodiments, detergents are effective in suspending harmful products that form in the lubricating oil composition during engine use.

[0200] The one or more detergents may be present at from about 0 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 0.2 wt % to about 4 wt %, based on the total weight of the lubricating oil composition.

[0201] Molybdenum-containing ingredients The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0202] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan 822™, Molyvan™ A, Molyvan 2000™, Molyvan 1055™, and Molyvan 855™ from R.T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0203] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0204] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula Mo3S k L n Q z and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms among all of the ligand's organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, incorporated herein by reference in its entirety.

[0205] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppmw to about 2000 ppmw, from about 1 ppmw to about 700 ppmw, from about 1 ppmw to about 550 ppmw, from about 5 ppmw to about 300 ppmw, or from about 20 ppmw to about 250 ppmw of molybdenum.

[0206] Transition metal-containing compounds In another embodiment, the oil-soluble compound can be a transition metal-containing compound or metalloid. Transition metals can include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0207] In some embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for preparing the oil-soluble materials of the disclosed technology include various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzenesulfonates), or generally, reaction products of titanium compounds with various acidic substances to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0208] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricants or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0209] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0210] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or may be represented by the following formula:

[0211] [ka] wherein m+n=4, n ranging from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms, or a group of formula:

[0212] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; and R4 is selected from H, C6 to C8 25 and the carboxylic acid moiety of

[0213] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0214] In some embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 ppmw to 3000 ppmw by weight of titanium, or from 25 ppmw to about 1500 ppmw by weight of titanium, or from about 35 ppmw to about 500 ppmw by weight of titanium, or from about 50 ppmw to about 300 ppmw by weight of titanium.

[0215] Viscosity Index Improver The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. The viscosity index improver may also include star polymers, suitable examples of which are described in U.S. Patent Publication No. 2012 / 0101017(A1).

[0216] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0217] The total amount of viscosity index improver and / or dispersant viscosity index improver may be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0218] Other optional additives Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the foregoing additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0219] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0220] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0221] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0222] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, or from about 0.02 wt % to about 0.04 wt %, based on the final weight of the lubricating oil composition.

[0223] Suitable rust inhibitors can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil is free of rust inhibitors.

[0224] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0225] Generally speaking, suitable crankcase lubricants may contain additive components in the ranges listed in the table below.

[0226] [Table 2]

[0227] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition, with the remainder of the lubricating oil composition consisting of one or more base oils.

[0228] The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations, however, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). [Example]

[0229] The following examples illustrate, but do not limit, the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the art and obvious to those skilled in the art are within the spirit and scope of the present disclosure. All patents and publications cited herein are hereby fully incorporated by reference in their entirety.

[0230] Each of the lubricating oil compositions contained a major amount of base oil and a base conventional dispersant inhibitor (DI) package. The DI package contained conventional amounts of dispersants, antiwear additives, antioxidants, friction modifiers, antifoam agents, process oils, viscosity index improvers, and pour point depressants, as provided in Table 3 below. Specifically, the DI package contained a succinimide dispersant, a molybdenum-containing compound, an antioxidant, and an antifoam agent. The majority of the base oil was a blend of Group II and Group III base oils. The modified components are specified in the example tables and discussion below. All values ​​listed are stated as weight percent of the component in the lubricating oil composition (i.e., the active stock plus diluent oil, if any) unless otherwise specified.

[0231] [Table 3]

[0232] The lubricating oil compositions were tested according to the Sequence VH Engine Test. The Sequence VH Test (ASTM D8256) is a test method used to evaluate engine deposit control by automotive engine oils under operating conditions intentionally selected to accelerate deposit formation. The engine is a gasoline-fueled, spark-ignition engine operated under low-temperature, light-load conditions. A 2013 Ford 4.6L fuel-injected, 8-cylinder gasoline engine equipped with roller followers, coolant-jacketed rocker covers, and a camshaft baffle was used.

[0233] The test duration was 216 hours, including 54 cycles, each consisting of three distinct operating phases as shown in Table 4 below: A fuel containing sludge precursors was used to intentionally increase engine blow-by, and rocker cover jacket temperatures were cycled.

[0234] [Table 4]

[0235] Sludge deposits are evaluated on the rocker arm covers, rocker arm cover baffles, timing chain cover, oil pan baffle, oil pan, and valve deck.

[0236] One of the measurements included in the Sequence VH test is a measurement of average engine sludge. Engine cleanliness is measured by sludge merit, with higher scores indicating a cleaner engine. An oil passes the average engine sludge test in 7.01 minutes or greater. The results of the average engine sludge test are shown in Table 5 below.

[0237] [Table 5] a) TBN of the lubricating oil composition to TBN contribution of all dispersants b) wt% phosphorus from ZDDP x TBN of the lubricating oil composition toTotal dispersant TBN contribution (P × TBNDisp − col 2 × col 4) c) wt% zinc from ZDDP x TBN of the lubricating oil composition to Total dispersant TBN contribution (Zn × TBNDisp-col 3 × col 4)

[0238] The data in Table 5 are plotted in the graph of Figure 1. The data in Table 5 and the graph of Figure 1 are based on the total base number (TBN) of a lubricating oil composition containing one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants. to The amount of zinc (Zn) by weight percent provided to the lubricating oil composition by one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants has a multiplication factor Zn of at least about 0.06. * TBNDisp demonstrates that there is improved cleanliness for the lubricating oil compositions, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0239] The data in Table 5 also show that at least about 0.06 wt. % Zn * Improved cleanliness exists for lubricating oil compositions formulated with the TBNDisp Multiplication Index, demonstrating that the amount of zinc provided by one or more ZDDP compounds ranges from 0.070 wt. % to 0.11 wt. %, based on the total weight of the lubricating oil composition, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0240] In addition, the data in Table 5 also show the weight percent Zn * The TBNDisp multiplication index of the lubricating oil composition is at least about 0.06, and toThis demonstrates that there is improved cleanliness for lubricating oil compositions formulated such that the TBN contribution of one or more dispersants is at least 0.79 mg KOH / g, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0241] The data in Table 5 are also plotted in the graph of Figure 2. The data in Table 5 and the graph of Figure 2 are based on lubricating oil compositions containing one or more zinc dialkyldithiophosphates (ZDDP compounds) and one or more dispersants, and the total base number (TBN) of the lubricating oil composition. to The weight percent amount of phosphorus (P) provided to the lubricating oil composition by the one or more ZDDPs multiplied by the TBN contribution of the one or more dispersants is a multiplication index P of at least about 0.051 by weight percent. * TBNDisp demonstrates that there is improved cleanliness for the lubricating oil compositions, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0242] The data in Table 5 and Figure 2 also show the weight percent P * The improved cleanliness is demonstrated for lubricating oil compositions formulated with a TBNDisp Multiplication Index of at least about 0.051 and one or more ZDDP compounds present in an amount sufficient to provide greater than about 0.065 wt. % P, based on the total weight of the lubricating oil composition, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0243] In addition, the data in Table 5 and Figure 2 also show the weight percent P * The TBNDisp multiplication index of the lubricating oil composition is at least about 0.051, and toThis demonstrates that there is improved cleanliness for lubricating oil compositions formulated such that the TBN contribution of one or more dispersants is at least 0.79 mg KOH / g, as evidenced by the higher average engine sludge values ​​for Inventive Examples IE-1 to IE-7 when compared to the values ​​for Comparative Examples CE-1 to CE-4.

[0244] Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout the specification and claims, "a" and / or "an" and / or "the" can refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities, proportions, percentages, or other numerical values ​​should be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0245] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0246] It is further understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of the values ​​1, 2, 3, and 4, and any range of such values.

[0247] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range, or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. In other words, it is also further understood that any range between the endpoints within a broad range is also contemplated herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0248] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

Claims

1. 1. A lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition, the additive composition comprising: two or more zinc dialkyldithiophosphates (ZDDP compounds), wherein at least one of the two or more ZDDP compounds is derived from one or more primary alcohols; one or more dispersants present in an amount of 0.1 wt. % to 7 wt. %, based on the total weight of the lubricating oil composition, the one or more dispersants consisting of a dispersant derived from polyisobutylene succinic anhydride (PIBSA), each of the one or more dispersants having a total base number (TBN) of 10 mg KOH / g to 65 mg KOH / g as measured by the method of ASTM D2896, and the contribution of the TBN of all dispersants to the TBN of the lubricating oil composition is 0.79 mg KOH / g to 2.5 mg KOH / g; one or more calcium-containing detergents, the one or more calcium-containing detergents being present in an amount providing the lubricating oil composition with greater than 0.01 wt % calcium to 0.25 wt % calcium, based on the total weight of the lubricating oil composition, and the one or more calcium-containing detergents comprising a calcium sulfonate detergent; the weight percent amount of zinc (Zn) provided to the lubricating oil composition by the two or more ZDDPs multiplied by the TBN contribution of the one or more PIBSA-derived dispersants to the TBN of the lubricating oil composition is a multiplication index Zn of 0.06 to 0.4; ＊ TBNDisp. lubricating oil composition.

2. The multiplication exponent Zn ＊ 2. The lubricating oil composition of claim 1, wherein TBNDisp is greater than 0.

07.

3. 10. The lubricating oil composition of claim 1, wherein the two or more ZDDP compounds are present in an amount sufficient to provide greater than 0.071 wt. % zinc, based on the total weight of the lubricating oil composition.

4. 1. A lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition, the additive composition comprising: two or more zinc dialkyldithiophosphates (ZDDP compounds), wherein at least one of the two or more ZDDP compounds is derived from one or more primary alcohols; one or more dispersants present in an amount of 0.1 wt. % to 7 wt. %, based on the total weight of the lubricating oil composition, the one or more dispersants consisting of a dispersant derived from polyisobutylene succinic anhydride (PIBSA), each of the one or more dispersants having a total base number (TBN) of 10 mg KOH / g to 65 mg KOH / g as measured by the method of ASTM D2896, and the contribution of the TBN of all dispersants to the TBN of the lubricating oil composition is 0.79 mg KOH / g to 2.5 mg KOH / g; one or more calcium-containing detergents, the one or more calcium-containing detergents being present in an amount providing the lubricating oil composition with greater than 0.01 wt % calcium to 0.25 wt % calcium, based on the total weight of the lubricating oil composition, and the one or more calcium-containing detergents comprising a calcium sulfonate detergent; the weight percent amount of phosphorus (P) provided to the lubricating oil composition by the two or more ZDDPs multiplied by the TBN contribution of the one or more PIBSA-derived dispersants to the TBN of the lubricating oil composition is a multiplication index P of 0.051 to 0.5; ＊ TBNDisp. lubricating oil composition.

5. The multiplication exponent P ＊ The lubricating oil composition of claim 4, wherein TBNDisp is greater than 0.06 to 0.

5.

6. 5. The lubricating oil composition of claim 4, wherein the two or more ZDDP compounds are present in an amount sufficient to provide greater than 0.065 wt. % P, based on the total weight of the lubricating oil composition.

7. 2. The lubricating oil composition of claim 1, wherein at least one of the two or more ZDDP compounds is derived from one or more secondary alkyl alcohols having an alkyl group having from 3 to 8 carbon atoms.

8. 5. The lubricating oil composition of claim 4, wherein at least one of the two or more ZDDP compounds is derived from one or more secondary alkyl alcohols having an alkyl group having from 3 to 8 carbon atoms.

9. 2. The lubricating oil composition of claim 1, wherein the two or more ZDDP compounds comprise a mixture of the one or more zinc dialkyldithiophosphates (ZDDPs) derived from a primary alcohol and a zinc dialkyldithiophosphate (ZDDP) derived from a secondary alcohol.

10. 5. The lubricating oil composition of claim 4, wherein the two or more ZDDP compounds comprise a mixture of the one or more zinc dialkyldithiophosphates (ZDDPs) derived from a primary alcohol and a zinc dialkyldithiophosphate (ZDDP) derived from a secondary alcohol.

11. 10. The lubricating oil composition of claim 9, wherein the ZDDP derived from one or more primary alcohols contributes 15 ppmw to 500 ppmw of zinc and the ZDDP derived from one or more secondary alcohols contributes 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

12. 11. The lubricating oil composition of claim 10, wherein the ZDDP derived from one or more primary alcohols contributes 15 ppmw to 500 ppmw of zinc and the ZDDP derived from one or more secondary alcohols contributes 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

13. 10. The lubricating oil composition of claim 1, wherein the PIBSA has an average of between 1.0 and 2.0 succinic acid moieties per polyisobutylene (PIB) polymer.

14. 5. The lubricating oil composition of claim 4, wherein the PIBSA has an average of between 1.0 and 2.0 succinic acid moieties per polyisobutylene (PIB) polymer.

15. 10. The lubricating oil composition of claim 1, wherein the one or more dispersants derived from a PIBSA are a mixture of at least one dispersant that has been post-treated by reaction with an agent selected from boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbyl-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, phosphorus compounds, and mixtures thereof, and at least one dispersant that has not been post-treated.

16. 5. The lubricating oil composition of claim 4, wherein the one or more dispersants derived from a PIBSA are a mixture of at least one dispersant that has been post-treated by reaction with an agent selected from boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbyl-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, phosphorus compounds, and mixtures thereof, and at least one dispersant that has not been post-treated.

17. 10. A method for reducing engine sludge in an internal combustion engine, comprising adding to the engine the lubricating oil composition of claim 1 and operating the engine, wherein the lubricating oil composition provides an average engine sludge test (ASTM D8256) result of 7.01 minutes or greater.

18. 10. A method for reducing engine sludge in an internal combustion engine, comprising adding to the engine the lubricating oil composition of claim 4 and operating the engine, wherein the lubricating oil composition provides an average engine sludge test (ASTM D8256) result of 7.01 minutes or greater.

19. 10. A method for improving fuel economy and / or piston cleanliness performance of an engine and / or vehicle, comprising providing to said engine and / or said vehicle the lubricant composition of claim 1.

20. 10. A method for improving fuel economy and / or piston cleanliness performance of an engine and / or vehicle, comprising providing to said engine and / or said vehicle the lubricant composition of claim 4.

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