Lubricating oil composition with resistance to engine deposits

Abstract

The present invention provides a lubricant composition having a desirable viscosity profile, including good low-temperature viscosity characteristics. Furthermore, it provides a lubricant composition that exhibits good dispersion characteristics without requiring the high dispersant treatment rate typically associated with high-performance engine oils. [Solution] A lubricating oil composition comprising a base oil with a lubricating viscosity of more than 50% by weight and an additive composition, wherein the additive composition comprises one or more zinc dialkyldithiophosphate (ZDDP compounds) and one or more dispersants, and the amount of zinc (Zn) by weight percentage provided to the lubricating oil composition by the one or more ZDDPs, multiplied by the amount of contribution of the TBN of the one or more dispersants to the total base number (TBN) of the lubricating oil composition, is at least about 0.06 multiplication exponent Zn * A lubricating oil composition, which is TBNDisp, is provided.

Description

[Technical Field]

[0001] This disclosure relates to an engine lubricant having good oxidation resistance and dispersibility for reducing engine deposits. In particular, this disclosure relates to a lubricant and a method for improving the lubricant's resistance to deposits in engines or other machine parts lubricated with the lubricant. The lubricant of this disclosure is useful as an internal combustion engine oil or in other applications where the lubricant is subjected to thermal and oxidizing conditions. [Background technology]

[0002] Lubricant compositions used in internal combustion engines should preferably exhibit good oxidation resistance, dispersibility, and tolerance to soot and sludge, to which they are inevitably exposed during their lifespan. Good dispersibility can extend the useful life of a lubricant composition, for example, by reducing the viscosity of the lubricant composition induced by soot, or by reducing the accumulation of sludge in the lubricant composition; otherwise, it can lead to a rapid loss of fuel economy. Typically, the dispersibility of a lubricant composition is improved by the addition of dispersants. Dispersants may constitute a significant proportion of the lubricant composition, and therefore, they represent a considerable cost component of the lubricant composition.

[0003] Furthermore, oxidation of molecules in lubricating oil can cause oligomerization, ultimately leading to a dramatic and irreversible increase in oil viscosity. Such an increase in oil viscosity can impair engine operation and reduce efficiency.

[0004] Therefore, in this technical field, there is a need for lubricant compositions having a desirable viscosity profile, including good low-temperature viscosity characteristics. Furthermore, there is a need for lubricant compositions that exhibit good dispersion characteristics without requiring the high dispersant treatment rate typically associated with high-performance engine oils. [Overview of the Initiative]

[0005] This disclosure satisfies the aforementioned need in the art for lubricant compositions having a desirable viscosity profile, including good low-temperature viscosity characteristics. This disclosure also satisfies the need for lubricant compositions that exhibit good dispersion characteristics without requiring the high dispersant treatment rate typically associated with high-performance engine oils.

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

[0007] 1. In a first aspect, the present disclosure provides a lubricating oil composition comprising a base oil having a lubricating viscosity of more than 50% by weight and an additive composition, wherein the additive composition is A compound comprising one or more zinc dialkyldithiophosphate (ZDDP) compounds and one or more dispersants, wherein the amount of zinc (Zn) provided to the lubricating oil composition by 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 at least about 0.06 multiplier exponent Zn * This relates to a lubricating oil composition, TBNDisp.

[0008] 2. Multiplication exponent Zn * The lubricating oil composition according to Document 1, wherein TBNDisp may be greater than about 0.07, or about 0.07 to 0.4, or about 0.075 to about 0.2.

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

[0010] 4. Multiplication exponent Zn *TBNDisp may be at least about 0.06, and the contribution of the TBN of one or more dispersants to the TBN of the lubricating oil composition is at least 0.79 mgKOH / g, or the multiplication index Zn * The lubricating oil composition according to any one of the preceding paragraphs, wherein TBNDisp is greater than about 0.07 and the contribution of the TBN of one or more dispersants to the TBN of the lubricating oil composition is at least 0.85 mgKOH / g.

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

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

[0013] 7. Multiplication index P * TBNDisp may be at least about 0.051, and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.065% by weight of P based on the total weight of the lubricating oil composition, or the multiplication index P25]] * The lubricating oil composition according to any one of paragraphs 5 to 6, wherein TBNDisp is greater than about 0.06 to 0.5 and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.07% by weight of P based on the total weight of the lubricating oil composition.

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

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

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

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

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

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

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

[0021] 15. A lubricating oil composition according to any one of paragraphs 1-4, 9, 11, and 13, wherein 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 isobutylcarbinol.

[0022] 16. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, and 14, wherein 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 isobutylcarbinol.

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

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

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

[0026] 20. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, 14, 16, and 18, wherein 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 according to Article 19, wherein the mixture may contain, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 15 ppmw to 500 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 100 ppmw to 1000 ppmw of zinc, or the mixture may contain, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 100 ppmw to 400 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 300 ppmw to 700 ppmw of zinc.

[0028] 22. The lubricating oil composition according to document 20, wherein the mixture may contain, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 15 ppmw to 500 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 100 ppmw to 1000 ppmw of zinc, or the mixture may contain, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 100 ppmw to 400 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 300 ppmw to 700 ppmw of zinc.

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

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

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

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

[0033] 27. A lubricating oil composition according to any one of paragraphs 1-4, 9, 11, 13, 15, 17, 19, 21, 23, and 25, wherein one or more ZDDP compounds may 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-penyl alcohol, hexanol, methyl isobutylcarbinol, isohexanol, n-heptanol, isoheptanol, octanol, amyl alcohol, and 2-ethylhexanol.

[0034] 28. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, 14, 16, 18, 20, 22, 24, and 26, wherein one or more ZDDP compounds may 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-penyl alcohol, hexanol, methyl isobutylcarbinol, isohexanol, n-heptanol, isoheptanol, octanol, amyl alcohol, and 2-ethylhexanol.

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

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

[0037] 31. A lubricating oil composition according to any one of articles 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, and 29, wherein 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 in the range of 100:20 to 50:50.

[0038] 32. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30, wherein 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 in a ratio of 100:20 to 50:50.

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

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

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

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

[0043] 37. A lubricating oil composition according to any one of paragraphs 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, and 35, wherein one or more dispersants may include 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 5,000 g / mol, or about 500 g / mol to about 3,000 g / mol, as measured by GPC.

[0044] 38. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36, wherein one or more dispersants may include 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 5,000 g / mol, or about 500 g / mol to about 3,000 g / mol, as measured by GPC.

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

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

[0047] 41. A lubricating oil composition according to any one of the articles 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, and 39, wherein 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) congeners and mixtures thereof, or one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylamine hexamine (PEHA), or 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. A lubricating oil composition according to any one of paragraphs 5-8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, and 40, wherein 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) congeners and mixtures thereof, or one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylamine hexamine (PEHA), or 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. A lubricating oil composition according to any one of the articles 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39 and 41, wherein one or more dispersants may contain 0.1% to 5% by weight of nitrogen, or 0.25% to 3% by weight of nitrogen, or 0.5% to 2% by weight of nitrogen, based on the total weight of one or more dispersants.

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

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

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

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

[0054] 48. A lubricating oil composition according to any one of paragraphs 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 one or more dispersants may have a TBN of about 10 mg KOH / g to about 65 mg KOH / g, measured by the method of ASTM D2896, based on an oil-free state.

[0055] 49. A lubricating oil composition according to any one of the following texts: 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, and 47, wherein the contribution of the total dispersant to TBN in the lubricating oil composition is at least 0.79 mg KOH / g, or at least 0.85 mg KOH / g, or 0.85 mg KOH / g to 5 mg KOH / g, or 0.9 mg KOH / g to 2.5 mg KOH / g.

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

[0057] 51. A lubricating oil composition according to any one of the following texts 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, and 49, wherein one or more dispersants may include at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, carbonate, cyclic carbonate, hindered phenol ester, phosphorus compounds, and mixtures thereof, or where one or more dispersants include at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0058] 52. A lubricating oil composition according to any one of paragraphs 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 one or more dispersants may include at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, carbonate, cyclic carbonate, hindered phenol ester, phosphorus compounds, and mixtures thereof, or where one or more dispersants include at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0059] 53. A lubricating oil composition according to any one of the articles 1-4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49 and 51, wherein one or more dispersants may be a mixture of at least one post-treated dispersant and at least one unpost-treated dispersant.

[0060] 54. A lubricating oil composition according to any one of paragraphs 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 one or more dispersants may be a mixture of at least one post-treated dispersant and at least one unpost-treated dispersant.

[0061] 55. A lubricating oil composition according to any one of paragraphs 1-4, 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 one or more dispersants is about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 7% by weight, based on the total weight of the lubricating oil composition.

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

[0063] 57. A lubricating oil composition according to any one of the following texts 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, anti-wear agents, defoamers, molybdenum-containing compounds, titanium-containing compounds, phosphorus-containing compounds, pour point depressants, and diluents.

[0064] 58. A lubricating oil composition according to any one of the articles 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, anti-wear agents, defoamers, molybdenum-containing compounds, titanium-containing compounds, phosphorus-containing compounds, pour point depressants, and diluents.

[0065] 59. A lubricating oil composition according to any one of the articles 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 can provide an average engine sludge test (ASTM D8256) result of 7.01 minutes or more, or 7.05 minutes or more, or 7.05 minutes to about 15 minutes.

[0066] 60. A lubricating oil composition according to any one of the articles 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 can provide an average engine sludge test (ASTM D8256) result of 7.01 minutes or more, or 7.05 minutes or more, or 7.05 minutes to about 15 minutes.

[0067] 61. A method for reducing engine sludge in an internal combustion engine, comprising adding a lubricating oil composition described in any one of the following documents: 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 to the engine, and operating the engine.

[0068] 62. A method for reducing engine sludge in an internal combustion engine, comprising adding a lubricating oil composition described in any one of the following documents: 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 to the engine, and operating the engine.

[0069] 63. A method for improving the fuel efficiency and / or piston cleaning performance of an engine and / or vehicle, comprising the step of providing the engine and / or vehicle with a lubricating oil composition described in any one of the documents 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 the fuel efficiency and / or piston cleaning performance of an engine and / or vehicle, comprising the step of providing the engine and / or vehicle with a lubricating oil composition described in any one of the documents 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.

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

[0072] The terms “oil composition,” “lubrication composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricating composition,” “completely formulated lubricant composition,” “lubricant,” “crankcase oil,” “crankcase lubricant,” “engine oil,” “engine lubricant,” “motor oil,” and “motor lubricant” are considered synonymous, fully interchangeable technical terms referring to the final lubrication product which contains a small amount of additive composition in addition to a main amount of base oil.

[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, fully interchangeable technical terms referring to a portion of a lubricating oil composition excluding the main amount of base oil raw material mixture. An additive package may or may not contain viscosity index modifiers or pour point depressants.

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

[0075] As used herein, the terms “hydrocarbyl substituent” or “hydrocarbyl group” are used in their ordinary sense, as is well known to those skilled in the art. Specifically, they refer to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon characteristics. Each hydrocarbyl group is independently selected from the hydrocarbon substituents, the substituted hydrocarbon substituents comprising one or more of the following: halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents present for every 10 carbon atoms in the hydrocarbyl group.

[0076] As used herein, the terms “hydrocarbilene substituent” or “hydrocarbilene group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups that are directly bonded to the rest of the molecule by carbon atoms at two locations on the molecule and that have primarily hydrocarbon characteristics. Each hydrocarbilene group is independently selected from divalent hydrocarbon substituents, the substituted divalent hydrocarbon substituents include halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbilene group.

[0077] As used herein, the term “weight percent” means the percentage of the listed ingredient relative to the total weight of the composition, unless otherwise explicitly stated.

[0078] As used herein, the terms “soluble,” “oil-soluble,” and “dispersible” may indicate, but do not necessarily, that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion. However, the aforementioned terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to a degree sufficient to exert their intended effect, for example, in an environment where oil is used. Furthermore, if desired, it may be possible to incorporate other additives to incorporate a higher level of specific additive properties.

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

[0080] As used herein, the term "alkyl" refers to linear, branched, cyclic, and / or substituted saturated chain portions comprising approximately 1 to 100 carbon atoms.

[0081] As used herein, the term “alkenyl” refers to a linear, branched, cyclic, and / or substituted unsaturated chain portion consisting of approximately 3 to 10 carbon atoms.

[0082] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms, including nitrogen, oxygen, and sulfur.

[0083] The lubricants, combinations of components, or individual components described 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. Internal combustion engines may be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel-fueled engines, mixed diesel / biofuel-fueled engines, mixed gasoline / biofuel-fueled engines, alcohol-fueled engines, mixed gasoline / alcohol-fueled engines, compressed natural gas (CNG)-fueled engines, or mixtures thereof. Diesel engines may be compression-ignition engines. Gasoline engines may be spark-ignition engines. Internal combustion engines may also be used in combination with electric or battery power sources. Engines configured in this way are usually known as hybrid engines. Internal combustion engines may be two-stroke, four-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (such as those for inland vessels), aircraft piston engines, low-duty diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks.

[0084] An internal combustion engine may contain one or more components from aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and / or mixtures thereof. Components may be coated, for example, with diamond-like carbon coatings, lubricating coatings, phosphorus-containing coatings, molybdenum-containing coatings, graphite coatings, nanoparticle-containing coatings, and / or mixtures thereof. Aluminum alloys may contain 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 containing aluminum and another component mixed or reacted at a microscopic or near-microscopic level, regardless of its detailed structure. This includes not only conventional alloys having metals other than aluminum, but also composite or alloy-like structures having nonmetallic elements or compounds such as ceramic-like materials.

[0085] Lubricating oil compositions 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% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less, or about 0.3% by weight or less, or about 0.2% by weight or less. In one embodiment, the sulfur content may be in the range of about 0.001% by weight to about 0.5% by weight, or about 0.01% by weight to about 0.3% by weight. The phosphorus content may be about 0.2% by weight or less, or about 0.1% by weight or less, or about 0.06% by weight or less, or about 0.2% by weight. 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 engine oil, and the lubricating oil composition may have (i) a sulfur content of about 0.5% by weight or less, (ii) a phosphorus content of about 0.1% by weight or less, and (iii) a sulfated ash content of about 1.5% by weight or less.

[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 the fuel used to power the marine engine and the high TBN required for marine-suitable engine oil (e.g., more than about 40 TBN for marine-suitable engine oil).

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

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

[0090] Furthermore, the lubricants described herein 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 (trademark), Dexos2 (trademark), 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.It may be suitable for meeting the original equipment manufacturer's specifications such as 5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specifications not described 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 fluids” is a term encompassing a wide range of fluids, including but not limited to tractor working fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, working fluids including tractor working fluids, some gear oils, power steering fluids, fluids used in wind turbines and compressors, some industrial fluids, and fluids associated with components of power transmission systems. It should be noted that within each of these fluids, such as automatic transmission fluids, there are various different types of fluids for various transmissions with different designs that require fluids with significantly different functional characteristics. This is in contrast to the term “lubricating fluids” which are not used for power generation or transmission.

[0092] For example, with respect to the working fluids of a tractor, these fluids are general-purpose fluids used for all lubrication applications of the tractor, except for lubricating the engine. These lubrication applications may include lubrication of the gearbox, power take-off and clutch, rear axle, reduction gear, wet brakes, and hydraulic accessories.

[0093] If the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, the coefficient of friction of a fluid tends to decrease due to the effect of temperature as the fluid heats up during operation. It is important for the working fluid or automatic transmission fluid of a tractor to maintain a high coefficient of friction at high temperatures; otherwise, the braking 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 the performance of engine oil with the performance of transmissions, differentials, final drive planetary gears, wet brakes, and hydraulic systems. Many of the additives used to formulate UTTO or STUO fluids are functionally similar, but may have harmful effects if not properly incorporated. For example, some anti-wear and extreme-pressure additives used in engine oils can be highly corrosive to the copper components of hydraulic pumps. Detergents and dispersants used in gasoline or diesel engine performance may be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake squeal may lack the thermal stability required for engine oil performance. Each of these fluids, regardless of functionality, tractor, or lubrication, is designed to meet specific, stringent manufacturer requirements.

[0095] This disclosure provides novel lubricant blends formulated for use as crankcase lubricants for automobiles. This disclosure provides novel lubricant blends formulated for use as crankcase lubricants for 2T and / or 4T motorcycles. Embodiments of this disclosure may provide lubricants suitable for crankcase applications and having improved properties of air inclusion, alcohol fuel compatibility, oxidation prevention, wear resistance, biofuel compatibility, bubble reduction, friction reduction, fuel efficiency, pre-ignition prevention, rust prevention, sludge and / or soot dispersibility, piston cleaning, deposit formation, and water resistance.

[0096] The engine oils of this 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, 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 benefits of this disclosure are partially described below and / or may be acquired through the practice of this disclosure. These details and benefits may be realized and achieved through the elements and combinations specifically indicated in the attached claims. It should be understood that both the general description above and the detailed description below are illustrative and descriptive only and do not limit the claimed disclosure. [Brief explanation of the drawing]

[0098] [Figure 1] This graph shows the amount of weight percent zinc (Zn) provided to a lubricating oil composition by one or more ZDDPs versus the average engine sludge, multiplied by the contribution of one or more dispersants to the total base number (TBN) of the lubricating oil composition. [Figure 2]This graph shows the amount of weight percentage phosphorus (P) provided to a lubricating oil composition by one or more ZDDPs versus the average engine sludge, multiplied by the contribution of one or more dispersants to the total base number (TBN) of the lubricating oil composition. [Modes for carrying out 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 lubricating oil's resistance to deposits in engines or other machine parts lubricated with the lubricating oil. The lubricating oils of this disclosure are useful as passenger vehicle engine oil (PVEO) products, commercial vehicle engine oil (CVEO) products, or in other applications where the lubricating oil is subjected to thermal and oxidative conditions.

[0100] In one embodiment, the lubricating oil composition of the present invention comprises a base oil with a lubricating viscosity of more than 50% by weight, and an additive composition comprising one or more zinc dialkyldithiophosphate (ZDDP) compounds and one or more dispersants, wherein the amount of zinc (Zn) by weight percentage provided to the lubricating oil composition by 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 at least about 0.06 multiplier exponent Zn * This is TBNDisp.

[0101] In another embodiment, the lubricating oil composition of the present invention comprises a base oil with a lubricating viscosity of more than 50% by weight, and an additive composition comprising one or more zinc dialkyldithiophosphate (ZDDP compounds) and one or more dispersants, wherein the amount of phosphorus (P) by weight percentage provided to the lubricating oil composition by one or more ZDDPs is calculated by multiplying the amount of contribution of the TBN of the one or more dispersants to the total base number (TBN) of the lubricating oil composition by the amount of contribution of the TBN of the one or more dispersants by the TBN of the one or more ZDDPs, with a multiplication exponent P of at least about 0.051. * This is TBNDisp.

[0102] ZDDP possesses antioxidant and wear-resistant properties. While not bound by theory, ZDDP is thought to act as an antioxidant to minimize the formation of deposit precursors such as hydroperoxides and radicals. These species are reactive and attack the hydrocarbon base oils and additives that make up the lubricant, forming sludge, resins, varnishes, and hard deposits. Dispersants work in conjunction with ZDDP by keeping these entities suspended in the bulk lubricant. This not only results in improved deposit control but also minimizes abrasive wear and viscosity increase associated with particulate matter.

[0103] As will be discussed in detail below, the lubricating oil composition was tested according to the Sequence VH engine test. The Sequence VH test (ASTM D8256) is a test method used to evaluate the control of engine deposits by automotive engine oil under operating conditions intentionally selected to accelerate deposit formation. This 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 the average engine sludge measurement. Engine cleanliness is measured by sludge merit, with a higher score indicating a cleaner engine.

[0104] In one embodiment, the engine oil has a multiplication exponent of at least about 0.06 Zn * When combined with an additive composition having the characteristics of TBNDisp, and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.071% by weight of zinc based on the total weight of the lubricating oil composition, improved resistance to engine deposits is observed. This improvement is seen in engine oil formulations lacking these characteristics.

[0105] In another embodiment, the engine oil is multiplied by the exponent Zn *When compounded with an additive composition having a TBNDisp of at least about 0.06 and a TBN contribution of one or more dispersants to the TBN of the lubricating oil composition of at least 0.79 mgKOH / g, it exhibits improved resistance to engine deposits. This improvement is observed compared to engine oil formulations lacking these characteristics.

[0106] In yet another embodiment, the engine oil is multiplied by an exponent P of at least about 0.051. * When combined with an additive composition having the characteristics of TBNDisp, and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.065% by weight of P based on the total weight of the lubricating oil composition, improved resistance to engine deposits is observed. This improvement is seen in engine oil formulations lacking these characteristics.

[0107] In a further embodiment, the engine oil is multiplied by exponent P * When compounded with an additive composition having a TBNDisp of at least about 0.051 and a TBN contribution of one or more dispersants to the TBN of the lubricating oil composition of at least 0.79 mgKOH / g, it exhibits improved resistance to engine deposits. This improvement is observed compared to engine oil formulations lacking these characteristics.

[0108] base oil The base oils used in the lubricating oil compositions described 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 shown in Table 1 below.

[0109] [Table 1]

[0110] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic 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. It should be noted that Group III base oils are derived from mineral oils, but due to the rigorous processing these fluids undergo, their physical properties become very similar to those of some true synthetic oils such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II.

[0111] The base oils used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined oils, refined oils, and re-refined oils, as well as mixtures thereof.

[0112] Unrefined oils are derived from natural, mineral, or synthetic sources that undergo little to no further refining. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps that may result in an improvement in one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to a quality suitable for consumption may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0113] Refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same way as refined oil using the same or similar processes. Often, these oils are further processed by techniques that target the removal of spent additives and oil degradation 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, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffinic-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or completely hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0115] Useful synthetic lubricants include hydrocarbon oils, such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (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 lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0117] In another embodiment, the main amount of base oil contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and any combination of two or more of the aforementioned, but the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index modifiers in the composition.

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

[0119] Dispersant The lubricating oil composition further comprises one or more dispersants. Dispersants do not contain metals that form ash before being mixed into the lubricating oil composition and do not typically contribute to ash when added to the lubricant, and are therefore often called ashless dispersants. Ashless dispersants are characterized by polar groups being bonded to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituents 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 preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)).

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

[0121] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing a small amount of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching than conventional polyamine mixtures. The heavy polyamine preferably contains a polyamine oligomer containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and 120 to 160 grams of primary amine groups per equivalent weight.

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

[0123] Typically, PAMs contain 8.7 to 8.9 milliequivalents of primary amines per gram (115 to 112 equivalents per primary amine equivalent) and a total nitrogen content of approximately 33% to 34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain only a small amount of PEHA, but mainly contain oligomers with more than six nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

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

[0125] In one embodiment, the disclosure further includes at least one 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 5,000 g / mol, or about 500 g / mol to about 3,000 g / mol, as measured by GPC. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0126] In some embodiments, if polyisobutylene is included, the polyisobutylene may have a terminal double bond content exceeding 50 mol%, 60 mol%, 70 mol%, 80 mol%, or 90 mol%. Such PIBs are also called highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 g / mol to about 5000 g / mol, as measured by GPC, are suitable for use in embodiments of this disclosure. Conventional PIBs typically have 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 in the range of approximately 900 g / mol to approximately 3000 g / mol, as measured by GPC, may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 by Boerzel, et al. and U.S. Patent No. 5,739,355 by Gateau, et al. When HR-PIBs are used in the above-mentioned thermal ene reaction, they may result in a higher conversion rate and less precipitate formation during the reaction due to increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696.

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

[0129] The active ingredient percentage of alkenyl or alkyl succinic anhydride can be measured using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0130] The conversion rate of polyolefins is calculated from the percentage of active ingredients using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0131] Unless otherwise specified, all percentages are weight percent, and all molecular weights are number-average molecular weights measured by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number-average molecular weight of 180 g / mol to approximately 18,000 g / mol as a calibration standard).

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

[0133] The TBN of a suitable dispersant, when measured in a dispersant sample containing approximately 50% diluted oil, can range from approximately 10 mg / KOH / g to approximately 65 mg / KOH / g based on the oil-free state, which corresponds to a TBN of approximately 5 mg / KOH / g to approximately 30 mg / KOH / g. The TBN is measured by the method of ASTM D2896.

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

[0135] Suitable types of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically from ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described and / or commercially available in U.S. Patents No. 7,485,603; No. 7,786,057; No. 7,253,231; No. 6,107,257; and No. 5,075,383.

[0136] Alternatively, the hydrocarbyl moiety of hydrocarbyl-dicarboxylic acid or the anhydride of component A) may be derived from ethylene-alphaolefin copolymers. These copolymers consist of multiple ethylene units and multiple C3-C3 copolymers. 10 Contains alpha-olefin units. C3~C 10 The alpha-olefin unit may contain propylene units.

[0137] One suitable type of dispersant may 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 detail by U.S. Patent No. 3,634,515.

[0138] A suitable class of dispersant may also be a high molecular weight ester or a semi-ester amide.

[0139] Suitable dispersants can also be post-treated by conventional methods in reaction with any of the following agents: boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, 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. Patents 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entirety.

[0140] One or more dispersants may be a mixture of at least one post-treated dispersant and at least one untreated dispersant. The weight ratio of post-treated to untreated dispersants may be about 5:1 to about 1:15, or about 4:1 to about 1:10.

[0141] In addition to the post-treatment of carbonates and boric acid, the compounds may be post-treated or further post-treated by 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: Inorganic phosphoric acid or anhydrous (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980), Organophosphorus compounds (e.g., U.S. Patent No. 3,502,677); Phosphorus pentasulfide; Boron compounds as already mentioned above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); Carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,386); Epoxy polyepoxyates or thioepoxys (e.g., U.S. Patent Nos. 3,859,318 and 5,026,495); Aldehydes or ketones (e.g., U.S. Patent No. 3,458,530); Carbon disulfide (e.g., U.S. Patent No. 3,256,185); Glycidol (e.g., U.S. Patent No. 4,617,137); Urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619, 3,865,813, and UK Patent No. 1,065,595); Organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. 2,140,811); Alkenyl cyanides (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); Diketen (e.g., U.S. Patent No. 3,546,243); Diisocyanates (e.g., U.S. Patent No. 3,573,205); Arkansulton (e.g., U.S. Patent No. 3,749,695); 1,3-Dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); Alkoxylated alcohols or phenolic sulfates (e.g., U.S. Patent 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. Patent Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170); Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,140,811); Hydroxyprotected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); Lactams, thiolactams, thiolactones, or ditholactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460), Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390; 4,646,860, and 4,670,170); Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,440,811); Hydroxyprotected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); Lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); Cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459); Hydroxyaliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464, 4,521,318; 4,713,189); Oxidizing agents (e.g., U.S. Patent No. 4,379,064); A combination of phosphorus pentasulfide and polyalkylene polyamine (e.g., U.S. Patent No. 3,185,647); A combination of a carboxylic acid or aldehyde or ketone and sulfur or sulfur chloride (e.g., U.S. Patent No. 3,390,086, U.S. Patent No. 3,470,098); A combination of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564); Combinations of aldehydes and phenols (e.g., U.S. Patent Nos. 3,649,229, 5,030,249; 5,039,307); A combination of aldehydes and dithiophosphate O-diesters (e.g., U.S. Patent No. 3,865,740); A combination of hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Patent No. 4,554,086); A combination of hydroxyaliphatic carboxylic acid followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); A combination of hydroxyaliphatic carboxylic acids and subsequent aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); Formaldehyde and phenol, and subsequent glycolic acid combinations (e.g., U.S. Patent No. 4,699,724); A combination of a hydroxyaliphatic carboxylic acid or oxalic acid followed by a diisocyanate (e.g., U.S. Patent No. 4,713,191); A combination of phosphorus inorganic acids or anhydrides, or their partial or whole sulfur analogs, and boron compounds (e.g., U.S. Patent No. 4,857,214); A combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitroso aromatic amine, optionally followed by a boron compound, and then a glycolating agent (e.g., U.S. Patent No. 4,973,412); Combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); Combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492); Combinations of cyclic lactones and boron compounds (e.g., U.S. Patent Nos. 4,963,275 and 4,971,711). The above patents are incorporated herein by reference in their entirety.

[0142] One or more dispersants may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Other amounts of one or more dispersants that can be used may range from about 0.1% to about 15% by weight, or from about 0.1% to about 10% by weight, or from about 0.1% to about 8% by weight, or from about 1% to about 10% by weight, or from about 1% to about 8% by weight, or from about 1% to about 7% by weight, 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 composition of this disclosure for use in internal combustion engines to reduce engine sludge contains a certain amount of one or more zinc dialkyldithiophosphate (ZDDP compounds). One or more ZDDP compounds may also help improve the friction and wear properties of the lubricating oil composition.

[0144] One or more ZDDP compounds are present in the lubricating oil composition in amounts of about 0.01% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight, or about 0.1% to about 1.5% by weight, based on the total weight of the lubricating oil composition.

[0145] One or more ZDDP compounds may include primary alkyl alcohols, secondary alkyl alcohols, or ZDDPs derived from combinations of primary and secondary alkyl alcohols. The primary and secondary alkyl alcohols used to prepare 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 branching at the beta carbon compared to the hydroxyl group.

[0146] For example, an alcohol with a beta (β) carbon branching would have the hydroxyl group branched at the second carbon atom from the oxygen atom.

[0147] [ka]

[0148] Suitable examples of primary and secondary alkyl alcohols for use in the preparation of 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 prepare one or more ZDDP compounds in a lubricating oil composition may be about 1:5 to 2:1. One or more ZDDP compounds may have a P:Zn molar ratio of about 1.08 to 1.3, or about 1.08 to 1.2, or about 1.09 to about 1.15. In some embodiments, one or more ZDDP compounds may be overbasicated with zinc oxide.

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

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

[0152] Suitable alcohols for producing one or more ZDDP compounds may be primary alkyl alcohols, secondary alkyl alcohols, or mixtures 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 compounds are derived from at least two secondary alcohols. The alcohols may be branched, cyclic, or linear.

[0153] One or more ZDDP compounds may be oil-soluble salts of dihydrocarbyl dithiophosphate, and the formula is as follows:

[0154] [ka]

[0155] In the formula, 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 an alkyl portion and a cycloalkyl portion. Therefore, the portion may be, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, 4-methylpentyl, 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 carbon atoms per mole of phosphorus in a ZDDP compound can also be calculated by dividing the sum of the carbon atoms of the four alkyl groups R5 and R6, which are provided to the ZDDP compound by the alcohol used in its preparation, 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 2 moles of phosphorus per mole of ZDDP gives an average total number of carbon atoms per mole of phosphorus of 9.

[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.] In the formula, alc1, alc2, and alc3 each represent different alcohols used to produce the ZDDP compound, and mol% is the molar percentage of each alcohol present in the reaction mixture used to produce the ZDDP compound. "~etc." indicates that if more than three alcohols are used to produce the ZDDP compound, the formula can be extended to include each alcohol present in the reaction mixture.

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

[0159] Zinc dialkyldithiophosphate compounds may be prepared according to known techniques by first forming dialkyldithiophosphate (DDPA) by reaction, usually 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 prepare the subcompound, but oxides, hydroxides, and carbonates are most commonly used. The zinc dialkyldithiophosphate of component (i) may be prepared by a process such as the process generally described in U.S. Patent 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 about 100 to about 1500 ppmw of phosphorus, or about 100 ppmw to about 1000 ppmw of phosphorus, or about 200 ppmw to about 1300 ppmw of phosphorus, or about 300 ppmw to about 1200 ppmw of phosphorus, or 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, based on the total weight of the lubricating oil composition, about 10 ppmw of zinc to about 1500 ppmw of zinc, or about 100 ppmw of zinc to about 1300 ppmw of zinc, or about 600 ppmw of zinc to about 1200 ppmw of zinc.

[0162] The use of one or more ZDDP compounds derived from a molar ratio of primary alkyl alcohols to secondary alkyl alcohols of approximately 100:0 to approximately 0:100 unexpectedly provides increased viscosity control across a wide variety of ZDDP compounds compared to the same lubricating oil composition except that which does not contain any ZDDP compounds. 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] Furthermore, 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 molar ratios ranging from 100:0 to 0.2:1, or 10:1 to 0.4:1, or 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, except for those lacking ZDDP compounds.

[0164] The present invention may include basic ZDDP or overbasic ZDDP. The term basic ZDDP, or equivalent expression, is used herein to describe zinc salts in which the metal substituent is present in a stoichiometrically greater amount than the phosphate radical. For example, ordinary or neutral zinc phosphorodithioate has 2 equivalents (i.e., 1 mole) of zinc per 2 equivalents (i.e., 2 moles) of phosphorodithioate, while basic diorganozinc phosphorodithioate has more than 2 equivalents of zinc per 2 equivalents of phosphorodithioate.

[0165] For example, overbasication can be carried out using basic zinc compounds such as zinc oxide. The amount of basic base compound required to give the desired overbasication is not important. The essential factor is that there is a sufficient amount of zinc compound in the reaction mixture for the overbasication reaction. Although not absolutely essential, it has been found that the reaction proceeds more satisfactorily when a slightly excess amount of zinc compound is used in addition to the amount required for the reaction. This excess should be kept to a minimum level to avoid the need to remove a large amount of solid from the final product. As a general rule, the excess zinc compound should not exceed 10-15% by weight.

[0166] Friction modifier The lubricating oil compositions described herein may optionally contain one or more friction modifiers. Suitable friction modifiers may include, but are not limited to, metal-containing and metal-free friction modifiers, and may include imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonic acids, metal-containing compounds, glycerol esters, sulfurized aliphatic 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. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. 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, di-ester, or (tri)glyceride. Friction modifiers may be long-chain fatty amides, long-chain fatty esters, long-chain fatty epoxide derivatives, or long-chain imidazolines.

[0168] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may contain esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic 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 whole in U.S. Patent No. 6,723,685, which is incorporated herein by reference.

[0169] Amineral friction modifiers may include amines or polyamines. Such compounds may have linear, saturated or unsaturated hydrocarbyl groups, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have linear, saturated or unsaturated hydrocarbyl groups, or mixtures thereof. They may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0170] Amines and amides may be used on their own or as 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 whole in U.S. Patent No. 6,300,291, which is incorporated herein by reference.

[0171] The friction modifier may optionally be present in a range such as approximately 0% to 10% by weight, approximately 0.01% to 8% by weight, or approximately 0.1% to 4% by weight.

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

[0173] Hindered phenol antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded 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, or 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, but may include, for example, Irganox® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate. The alkyl group may contain approximately 1 to 18 carbon atoms, or approximately 2 to 12 carbon atoms, or approximately 2 to 8 carbon atoms, or approximately 2 to 6 carbon atoms, or approximately 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, so that each antioxidant may be present in an amount sufficient to provide up to about 5% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the antioxidant may be a mixture of about 0.3% to about 1.5% by weight of diarylamine and about 0.4% to about 2.5% by weight of high molecular weight phenol, based on the final weight of the lubricating oil composition.

[0175] 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 may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester such as butyl acrylate.

[0176] Another classification of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain about 4 to 22 carbon atoms. Suitable examples of fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

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

[0178] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or from about 0.1% to about 10% by weight, or from about 1% to about 5% by weight.

[0179] Abrasion-resistant agent The lubricating oil compositions herein may also optionally contain one or more anti-wear agents in addition to one or more ZDDP compounds. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; phosphate esters or salts thereof; phosphate 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 anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0180] Further examples of suitable abrasion resistant agents include titanium compounds, tartarates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutylphosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartarates or tartrimides may contain alkyl-ester groups, where the total number of carbon atoms on the alkyl group is at least 8. In one embodiment, the abrasion resistant agent may include citrates.

[0181] The anti-wear agent may be present in the lubricating oil composition in an amount ranging from about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight.

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

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

[0184] If present, boron-containing compounds may be used in amounts sufficient to provide a maximum of about 8% by weight, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0185] Cleansing agent The lubricating oil composition may contain one or more detergents. These detergents may be neutral, low-basic, or over-basic detergents, or mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixalates, salixalates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for preparing them are described in more detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited herein.

[0186] One or more cleaning agents may be formed from cleaning agent substrates salted with alkali metals or other alkaline earth metals, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the cleaning agent does not contain barium.

[0187] Suitable cleaning agents include petroleum sulfonic acid and salts of long-chain mono- or di-alkylarylsulfonic acid in which the aryl group is benzyl, tolyl, or xylyl. Examples of suitable cleaning agents include, but are not limited to, calcium carbonate, sulfur-containing calcium carbonate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium carbonate, sulfur-containing magnesium carbonate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium carbonate, sulfur-containing sodium carbonate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

[0188] One or more cleaning agents may be overbasic cleaning agents. Such cleaning agent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

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

[0190] The overbasic detergent in the lubricating oil composition may have a total base number (TBN) of approximately 200 mg KOH / gram or more, or, as further examples, approximately 225 mg KOH / g or more, or approximately 250 mg KOH / gram or more, or approximately 300 mg KOH / gram or more, or approximately 350 mg KOH / gram or more, or approximately 375 mg KOH / gram or more, or approximately 400 mg KOH / gram or more.

[0191] Preferably, one or more cleaning agents include a cleaning agent containing overbasic calcium. Suitable examples of overbasic calcium-containing cleaning agents include, but are not limited to, overbasic calcium carbonate, overbasic sulfur-containing calcium carbonate, overbasic calcium sulfonate, overbasic calcium calixalate, overbasic calcium salixalate, overbasic calcium salicylate, overbasic calcium carboxylate, overbasic calcium phosphate, overbasic monothiophosphate and / or calcium dithiophosphate, overbasic calcium alkylphenol, overbasic calcium sulfur-bonded alkylphenol compounds, and overbasic calcium methylene crosslinked phenol. Preferably, the overbasic calcium-containing cleaning agent is an overbasic calcium sulfonate cleaning agent.

[0192] Other suitable examples of overbasic detergents include, but are not limited to, overbasic magnesium carbohydrate, overbasic sulfur-containing magnesium carbohydrate, overbasic magnesium sulfonate, overbasic magnesium calixalate, overbasic magnesium salixalate, overbasic magnesium salicylate, overbasic magnesium carboxylate, overbasic magnesium phosphate, overbasic mono- and / or di-thiophosphate magnesium, overbasic magnesium alkylphenol, overbasic magnesium sulfur-bonded alkylphenol compounds, or overbasic magnesium methylene crosslinked phenol.

[0193] The overbasic cleaning agent 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] One or more cleaning agents may be low-basic / neutral cleaning agents having a maximum of 175 mg KOH / g or a maximum of 150 mg KOH / g TBN. The low-basic / neutral cleaning agent may be formed from a cleaning agent substrate salted with an alkali metal or another alkaline earth metal, for example, but not limited to calcium, magnesium, potassium, sodium, lithium, barium, or a mixture thereof. In some embodiments, the cleaning agent does not contain barium. Low-basic / neutral cleaning agents may be selected from sulfonates, phenates, or salicylate cleaning agents. In some embodiments, the low-basic / neutral cleaning agent is a calcium-containing cleaning agent or a mixture of calcium-containing cleaning agents. In some embodiments, the low-basic / neutral cleaning agent is a calcium sulfonate cleaning agent or a calcium carbohydrate cleaning agent. In embodiments, one or more cleaning agents include a mixture of one or more low-basic / neutral calcium-containing cleaning agents and one or more overbasic calcium-containing cleaning agents.

[0195] One or more cleaning agents may include a cleaning agent containing overbasic calcium and a low-basic / neutral cleaning agent which is a salt of an alkali metal or alkaline earth metal other than calcium.

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

[0197] A low basic / neutral detergent may provide calcium in an amount constituting at least 0.001% by weight of the calcium provided by the total detergent in the lubricating oil composition. In some embodiments, the low basic / neutral detergent may provide calcium in an amount constituting at least 0.003% by weight, or 0.003% to 0.05% by weight, of the calcium provided by the total detergent in the lubricating oil composition.

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

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

[0200] One or more cleaning agents may be present in amounts of about 0% to about 10% by weight, or about 0.1% to about 8% by weight, or about 0.2% to about 4% by weight, based on the total weight of the lubricating oil composition.

[0201] Molybdenum-containing ingredients The lubricating oil compositions described herein may optionally also contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. 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 dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be 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 RTVanderbilt Co., Ltd., as well as commercially available materials sold under trade names such as Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Patent No. 5,650,381, U.S. Reissue Patents No. 37,363(E1), No. 38,929(E1), and No. 40,595(E1), which are incorporated herein by reference in their entirety.

[0203] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, compositions can provide molybdenum by molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patents 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 International Publication No. 94 / 06897, the aforementioned patent documents are incorporated herein by reference in their entirety.

[0204] Another class of suitable organomolybdenum compounds is trinuclear molybdenum compounds, for example, those of the formula Mo3S k L n Q z The compounds and mixtures thereof are, in the formula, S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to make 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-donating compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. In all ligand organic groups, there may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated in whole herein by reference.

[0205] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum in the ranges of approximately 0.5 ppmw to approximately 2000 ppmw, approximately 1 ppmw to approximately 700 ppmw, approximately 1 ppmw to approximately 550 ppmw, approximately 5 ppmw to approximately 300 ppmw, or approximately 20 ppmw to approximately 250 ppmw.

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

[0207] In some embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, friction modifier, antioxidant, adhesion 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 titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of oil-soluble materials of the art of this disclosure are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, e.g., titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, e.g., but not limited to titanium carboxylate; titanium carboxylates, e.g., titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolamine) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), such as titanium dithiophosphate, or reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic substances. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among other things. Ti compounds can also exist in dimer or oligomer forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques evident to those skilled in the art. Depending on the specific compound, they can exist as solids or liquids at room temperature. They can also be provided in solution form in a suitable inert solvent.

[0208] In one embodiment, titanium may be supplied as a Ti-modified dispersant such as a succinimide dispersant. Such a material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride such as alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of several substances, such as (a) a polyamine-based succinimide / amide dispersant having a free condensable -NH functional group; (b) a component of a polyamine-based succinimide / amide dispersant, i.e., alkenyl-(or alkyl) succinic anhydride and a polyamine; or (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, amino alcohol, polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to the lubricant, or it may be further reacted with a succinic acid dispersant as described above. For example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

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

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

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

[0212] [ka] (In the formula, x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing approximately 1 to 6 carbon atoms, and R4 is H, C6 to C) 25 It can be represented by (selected from the group consisting of any of the carboxylic acid moieties).

[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, and neodecanoic acid.

[0214] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount that provides 0 ppmw to 3000 ppmw of titanium, or 25 ppmw to about 1500 ppmw of titanium, or about 35 ppmw to about 500 ppmw of titanium, or about 50 ppmw to about 300 ppmw of titanium.

[0215] Viscosity index modifier The lubricating oil compositions of this specification may optionally contain one or more viscosity index modifiers. Suitable viscosity index modifiers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may also include star polymers, a preferred example of which is described in U.S. Patent Publication No. 2012 / 0101017(A1).

[0216] The lubricating oil compositions of this specification may optionally contain one or more dispersant viscosity index modifiers in addition to, or instead of, a viscosity index modifier. Suitable viscosity index modifiers 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 an amine.

[0217] Viscosity index modifier and / or dispersant. The total amount of viscosity index modifier may be about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 12% by weight, or 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 of the lubricating fluid. Furthermore, one or more of the aforementioned additives may be polyfunctional and may provide functions in addition to those described herein, or other functions.

[0219] Lubricant compositions according to this disclosure may optionally include other performance additives. These other performance additives may be additions to the specific additives of this disclosure and / or may include one or more of the following: metal deactivators, viscosity index modifiers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, viscosity index modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricant composition will contain one or more of these performance additives.

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

[0221] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

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

[0223] Suitable rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of 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 dimers and trimers, such as those derived 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 succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol such as polyglycol. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil does not contain rust inhibitors.

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

[0225] Generally speaking, a suitable crankcase lubricant may contain additive components within the range listed in the table below.

[0226] [Table 2]

[0227] The percentages for each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils.

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

[0229] The following examples illustrate, but are not limiting, the methods and compositions of the Disclosure. Various other suitable modifications and adaptations of conditions and parameters commonly encountered in the art and apparent to those skilled in the art are within the spirit and scope of the Disclosure. All patents and publications referenced herein are incorporated herein in their entirety by reference.

[0230] Each lubricating oil composition contained a primary amount of base oil and a base conventional dispersant inhibitor (DI) package. The DI package contained conventional amounts of dispersant, anti-wear additive, antioxidant, friction modifier, defoamer, process oil, viscosity index modifier, and pour point depressant, as provided in Table 3 below. Specifically, the DI package contained succinimide dispersant, molybdenum-containing compound, antioxidant, and defoamer. The majority of the base oil was a mixture of Group II and Group III base oils. Modified components are specified in the table and discussion of the examples below. All values ​​listed are expressed as weight percentages of the components in the lubricating oil composition (i.e., active ingredients plus diluent oil, if any), unless otherwise specified.

[0231] [Table 3]

[0232] The lubricating oil composition was tested according to the Sequence VH engine test. The Sequence VH test (ASTM D8256) is a test method used to evaluate the control of engine deposits by automotive engine oil 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 with roller followers, coolant-jacketed rocker covers, and camshaft baffles is used.

[0233] The test period was 216 hours, including 54 cycles, each consisting of three different operating phases as shown in Table 4 below: Using fuel containing sludge precursors to intentionally increase engine blow-by; and circulating the rocker cover jacket temperature.

[0234] [Table 4]

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

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

[0237] [Table 5] a) Contribution of TBN of the total dispersant to TBN in the lubricating oil composition b) Weight % of phosphorus from ZDDP × Contribution of TBN of the total dispersant to TBN in the lubricating oil composition (P × TBNDisp - col 2 × col 4) c) Weight % of zinc from ZDDP × Contribution of TBN of the total dispersant to TBN in the lubricating oil composition (Zn × TBNDisp-col 3 × col 4)

[0238] The data in Table 5 is plotted in the graph in Figure 1. The data in Table 5 and the graph in Figure 1 represent a lubricating oil composition comprising one or more dialkyldithiophosphate zinc (ZDDP compounds) and one or more dispersants, wherein the amount of zinc (Zn) provided to the lubricating oil composition by one or more ZDDPs, multiplied by the contribution of the TBN of one or more dispersants to the total base number (TBN) of the lubricating oil composition, is at least about 0.06 multiplier exponent Zn * TBNDisp demonstrates improved cleanliness in its lubricating oil compositions. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to Comparative Examples CE-1 to CE-4.

[0239] The data in Table 5 also shows the multiplication exponent of Zn by weight % at least about 0.06. * Lubricant compositions formulated using TBNDisp exhibit improved cleanliness, demonstrating that the amount of zinc provided by one or more ZDDP compounds is 0.070% to 0.11% by weight based on the total weight of the lubricant composition. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to Comparative Examples CE-1 to CE-4.

[0240] In addition, the data in Table 5 also shows the multiplication exponent Zn by weight %. *We demonstrate that improved cleanliness exists for lubricating oil compositions formulated such that TBNDisp is at least about 0.06 and the contribution of one or more dispersants to TBN in the lubricating oil composition is at least 0.79 mgKOH / g. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to the values ​​of Comparative Examples CE-1 to CE-4.

[0241] The data in Table 5 is also plotted in the graph in Figure 2. The data in Table 5 and the graph in Figure 2 represent a lubricating oil composition comprising one or more zinc dialkyldithiophosphate (ZDDP) compounds and one or more dispersants, wherein the amount of phosphorus (P) provided to the lubricating oil composition by one or more ZDDPs, multiplied by the contribution of the TBN of one or more dispersants to the total base number (TBN) of the lubricating oil composition, is at least about 0.051, with a multiplication index of weight percent P * TBNDisp demonstrates improved cleanliness in its lubricating oil compositions. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to Comparative Examples CE-1 to CE-4.

[0242] The data in Table 5 and Figure 2 are also multiplied by the weight % exponent P * The TBNDisp is at least about 0.051, and improved cleanliness is demonstrated for lubricating oil compositions formulated so that one or more ZDDP compounds are present in sufficient quantities to provide more than about 0.065% by weight of P based on the total weight of the lubricating oil composition. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to the values ​​of Comparative Examples CE-1 to CE-4.

[0243] In addition, the data in Table 5 and Figure 2 also multiplies by the weight % exponent P. *We demonstrate that improved cleanliness exists for lubricating oil compositions formulated such that TBNDisp is at least about 0.051 and the contribution of one or more dispersants to TBN in the lubricating oil composition is at least 0.79 mgKOH / g. This is evident from the higher average engine sludge values ​​of Examples IE-1 to IE-7 of the present invention compared to the values ​​of Comparative Examples CE-1 to CE-4.

[0244] Other embodiments of this disclosure will become apparent to those skilled in the art from consideration of this specification and the practice of the embodiments disclosed herein. Where used throughout the specification and claims, “a” and / or “an” and / or “the” may refer to one or more. Unless otherwise indicated, all numbers representing quantities, proportions, percentages, or other numerical values ​​should in all cases be understood as being modified by the term “about.” Thus, unless otherwise indicated, numerical parameters described herein and in the claims are approximations that may vary depending on the desired characteristics sought by this disclosure. At a minimum, each numerical parameter should be interpreted, not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, but at least in terms of the number of significant figures reported and by applying ordinary rounding techniques.

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

[0246] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1–4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as 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 and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0248] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in the description or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​of the range 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. A lubricating oil composition comprising a base oil with a lubricating viscosity of more than 50% by weight and an additive composition, wherein the additive composition is A lubricating oil composition comprising one or more zinc dialkyldithiophosphate (ZDDP) compounds and one or more dispersants, wherein the amount of zinc (Zn) by weight percentage provided to the lubricating oil composition by the one or more ZDDP compounds, 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 at least about 0.06 multiplication exponent Zn ＊ A lubricating oil composition that is TBNDisp.

2. The aforementioned multiplication exponent Zn ＊ The lubricating oil composition according to claim 1, wherein TBNDisp is greater than approximately 0.

07.

3. The aforementioned multiplication exponent Zn ＊ The lubricating oil composition according to claim 1, wherein TBNDisp is at least about 0.06, and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.071% by weight of zinc based on the total weight of the lubricating oil composition.

4. The aforementioned multiplication exponent Zn ＊ The lubricating oil composition according to claim 1, wherein TBNDisp is at least about 0.06, and the contribution of the one or more dispersants to TBN in the lubricating oil composition is at least 0.79 mgKOH / g.

5. A lubricating oil composition comprising a base oil with a lubricating viscosity of more than 50% by weight and an additive composition, wherein the additive composition is A lubricating oil composition comprising one or more zinc dialkyldithiophosphate (ZDDP compounds) and one or more dispersants, wherein the amount of phosphorus (P) by weight percentage 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 P of at least about 0.

051. ＊ A lubricating oil composition that is TBNDisp.

6. The aforementioned multiplication exponent P ＊ The lubricating oil composition according to claim 5, wherein TBNDisp is greater than 0.06 and 0.

5.

7. The aforementioned multiplication exponent P ＊ The lubricating oil composition according to claim 5, wherein TBNDisp is at least about 0.051, and one or more ZDDP compounds are present in an amount sufficient to provide more than about 0.065% by weight of P based on the total weight of the lubricating oil composition.

8. The aforementioned multiplication exponent P ＊ The lubricating oil composition according to claim 5, wherein TBNDisp is at least about 0.051, and the contribution of the one or more dispersants to TBN in the lubricating oil composition is at least 0.79 mgKOH / g.

9. The lubricating oil composition according to claim 1, wherein the one or more ZDDP compounds are derived from one or more secondary alkyl alcohols having an alkyl group having 3 to 8 carbon atoms.

10. The lubricating oil composition according to claim 5, wherein the one or more ZDDP compounds are derived from one or more secondary alkyl alcohols having an alkyl group having 3 to 8 carbon atoms.

11. The lubricating oil composition according to claim 1, wherein the one or more ZDDP compounds are a mixture of a total primary alcohol ZDDP compound and a total secondary alcohol ZDDP compound.

12. The lubricating oil composition according to claim 5, wherein the one or more ZDDP compounds are a mixture of a total primary alcohol ZDDP compound and a total secondary alcohol ZDDP compound.

13. The lubricating oil composition according to claim 11, wherein the mixture comprises, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 15 ppmw to 500 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 100 ppmw to 1000 ppmw of zinc.

14. The lubricating oil composition according to claim 12, wherein the mixture comprises, based on the mass of the lubricating oil composition, a total primary alcohol ZDDP compound contributing 15 ppmw to 500 ppmw of zinc and a total secondary alcohol ZDDP compound contributing 100 ppmw to 1000 ppmw of zinc.

15. The lubricating oil composition according to claim 1, wherein the one or more dispersants comprise at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), and the PIBSA has an average of about 1.0 and about 2.0 succinic acid portions per polyisobutylene (PIB) polymer molecule.

16. The lubricating oil composition according to claim 5, wherein the one or more dispersants comprise at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), and the PIBSA has an average of about 1.0 and about 2.0 succinic acid portions per polyisobutylene (PIB) polymer molecule.

17. The lubricating oil composition according to claim 1, wherein the contribution of the TBN of the total dispersant to the TBN in the lubricating oil composition is at least 0.79 mg KOH / g.

18. The lubricating oil composition according to claim 5, wherein the contribution of the TBN of the total dispersant to the TBN in the lubricating oil composition is at least 0.79 mg KOH / g.

19. The lubricating oil composition according to claim 1, wherein the one or more dispersants are a mixture of at least one post-treated dispersant and at least one untreated dispersant.

20. The lubricating oil composition according to claim 5, wherein the one or more dispersants are a mixture of at least one post-treated dispersant and at least one untreated dispersant.

21. A method for reducing engine sludge in an internal combustion engine, comprising adding the lubricating oil composition described in claim 1 to the engine and operating the engine.

22. A method for reducing engine sludge in an internal combustion engine, comprising adding the lubricating oil composition described in claim 5 to the engine and operating the engine.

23. A method for improving the fuel efficiency and / or piston cleaning performance of an engine and / or vehicle, comprising the step of providing the engine and / or vehicle with the lubricant composition described in claim 1.

24. A method for improving the fuel efficiency and / or piston cleaning performance of an engine and / or vehicle, comprising the step of providing the engine and / or vehicle with the lubricant composition described in claim 5.

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