Lubricating oil composition having resistance to engine deposits

Abstract

A lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and: a) an additive comprising: one or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants, wherein the weight percent of zinc (Zn) provided to the oil composition by the ZDDP compound multiplied by the total base number (TBN) of the dispersant contributes to the TBN of the oil composition by a multiplication factor Zn*TBNDisp of at least about 0.06; or b) an additive comprising one or more ZDDP compounds and one or more dispersants, wherein the weight percent of phosphorus (P) provided to the oil composition by the ZDDP compound multiplied by the total base number (TBN) of the dispersant contributes to the TBN of the oil composition by a multiplication factor P*TBNDisp of at least about 0.051.

Description

Technical Field

[0001] The present disclosure relates to engine lubricating oils having good oxidation resistance and dispersancy to reduce engine deposits. Specifically, the present disclosure relates to lubricating oils, and methods for improving the resistance of lubricating oils to deposits in engines or other mechanical parts lubricated by the lubricating oils. The lubricating oils of the present disclosure can be used as internal combustion engine oils or other applications where the lubricating oils are subjected to heat and oxidation conditions. Background Art

[0002] Lubricant compositions are expected to exhibit good oxidation resistance and dispersancy properties as well as tolerance to soot and sludge to which lubricant compositions employed in internal combustion engines are inevitably exposed during their service life. Good dispersancy can extend the service life of the lubricant composition, for example, by reducing soot-induced thickening of the lubricant composition, or by reducing sludge accumulation in the lubricant composition, which otherwise can rapidly lead to a loss of fuel economy. Typically, the dispersancy properties of a lubricant composition are improved by the addition of dispersants. A substantial portion of the lubricant composition may consist of dispersants, and therefore these dispersants represent a substantial cost component of the lubricant composition.

[0003] In addition, oxidation of molecules in the lubricating oil can cause oligomerization and ultimately lead to a significant, irreversible increase in oil viscosity. Such an increase in oil viscosity can both impede engine operation and reduce efficiency.

[0004] Therefore, there is a need in the art for lubricant compositions having desirable viscosity properties, including good low temperature viscosity properties. There is also a need for lubricant compositions that exhibit good dispersancy properties without requiring high dispersant treat rates, as are typically associated with high performance engine oils.

[0005] Summary and terminology

[0006] The present disclosure satisfies the above-mentioned need in the art for lubricant compositions having desirable viscosity properties, including good low temperature viscosity properties. The present disclosure also satisfies the need for lubricant compositions that exhibit good dispersion properties without requiring high dispersant treat rates, such as are typically associated with high performance engine oils.

[0007] The present disclosure can be described by the following sentences.

[0008] 1. In a first aspect, the present disclosure relates to a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising:

[0009] One or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants, wherein the amount of zinc (Zn) provided to the lubricating oil composition by the one or more ZDDP compounds multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor Zn*TBNDisp of at least about 0.06.

[0010] 2. The lubricating oil composition of statement 1, wherein the Zn*TBNDisp multiplication factor may be greater than about 0.07; or about 0.07 to 0.4; or about 0.075 to about 0.2.

[0011] 3. A lubricating oil composition according to any of the preceding sentences, wherein the Zn*TBNDisp multiplication factor may be at least about 0.06 and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.071 wt % zinc based on the total weight of the lubricating oil composition; or the Zn*TBNDisp multiplication factor is greater than about 0.07 and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.080 wt % zinc based on the total weight of the lubricating oil composition.

[0012] 4. A lubricating oil composition according to any of the preceding sentences, wherein the Zn*TBNDisp multiplication factor may be at least about 0.06, and the TBN of the one or more dispersants contributes at least 0.79 mgKOH / g to the TBN of the lubricating oil composition; or the Zn*TBNDisp multiplication factor is greater than about 0.07, and the TBN of the one or more dispersants contributes at least 0.85 mgKOH / g to the TBN of the lubricating oil composition.

[0013] 5. In a second aspect, the present disclosure is directed to a lubricating oil composition comprising greater than 50 wt. % of a base oil of lubricating viscosity and an additive composition comprising:

[0014] One or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants, wherein the amount of phosphorus (P) provided to the lubricating oil composition by the one or more ZDDP compounds multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor P*TBNDisp of at least about 0.051.

[0015] 6. The lubricating oil composition according to clause 5, wherein the P*TBNDisp multiplication factor may be greater than about 0.06 to 0.5; or about 0.07 to about 0.25.

[0016] 7. The lubricating oil composition of any one of clauses 5 to 6, wherein the P*TBNDisp multiplication factor can be at least about 0.051, and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.065 wt. % P based on the total weight of the lubricating oil composition; or the P*TBNDisp multiplication factor is greater than about 0.06 to 0.5, and the one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.07 wt. % P based on the total weight of the lubricating oil composition.

[0017] 8. A lubricating oil composition according to any one of clauses 5 to 7, wherein the P*TBNDisp multiplication factor can be at least about 0.051, and the TBN of the one or more dispersants contributes to the TBN of the lubricating oil composition by at least 0.79 mgKOH / g; or the P*TBNDisp multiplication factor is greater than about 0.06 to 0.5, and the TBN of the one or more dispersants contributes to the TBN of the lubricating oil composition by at least 0.85 mgKOH / g.

[0018] 9. The lubricating oil composition of any one of clauses 1 to 4, wherein the one or more ZDDP compounds are 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.

[0019] 10. The lubricating oil composition of any one of clauses 5 to 8, wherein the one or more ZDDP compounds are 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.

[0020] 11. The lubricating oil composition of any one of clauses 1 to 4 and 9, wherein the amount of the one or more dispersants may be greater than about 0.5 wt %; or 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 %, wherein the amount is based on the total weight of the lubricating oil composition.

[0021] 12. The lubricating oil composition of any one of clauses 5 to 8 and 10, wherein the amount of the one or more dispersants may be greater than about 0.5 wt %; or 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 %, wherein the amount is based on the total weight of the lubricating oil composition.

[0022] 13. The lubricating oil composition of any one of clauses 1 to 4, 9 and 11, wherein the one or more ZDDP compounds may be derived from one or more secondary alkyl alcohols having an alkyl group containing 3 to 8 carbon atoms.

[0023] 14. The lubricating oil composition of any one of clauses 5 to 8, 10 and 12, wherein the one or more ZDDP compounds may be derived from one or more secondary alkyl alcohols having an alkyl group containing 3 to 8 carbon atoms.

[0024] 15. The lubricating oil composition of any one of clauses 1 to 4, 9, 11 and 13, wherein the one or more ZDDP compounds may be derived from a secondary alkyl alcohol selected from the group consisting of isopropyl alcohol, amyl alcohol and methyl isobutyl carbinol.

[0025] 16. The lubricating oil composition of any one of clauses 5 to 8, 10, 12 and 14, wherein the one or more ZDDP compounds may be derived from a secondary alkyl alcohol selected from the group consisting of isopropanol, amyl alcohol and methyl isobutyl carbinol.

[0026] 17. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13 and 15, wherein the one or more ZDDP compounds can be derived from two or more secondary alkyl alcohols.

[0027] 18. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14 and 16, wherein the one or more ZDDP compounds can be derived from two or more secondary alkyl alcohols.

[0028] 19. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15 and 17, wherein the one or more ZDDP compounds can be a mixture of all-primary ZDDP compounds and all-secondary ZDDP compounds.

[0029] 20. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16 and 18, wherein the one or more ZDDP compounds can be a mixture of all-primary ZDDP compounds and all-secondary ZDDP compounds.

[0030] 21. The lubricating oil composition of clause 19, wherein the mixture may comprise an all-primary alcohol ZDDP compound that contributes 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition; or the mixture comprises an all-primary alcohol ZDDP compound that contributes 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 300 ppmw to 700 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

[0031] 22. The lubricating oil composition of clause 20, wherein the mixture may comprise an all-primary alcohol ZDDP compound that contributes 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition; or the mixture comprises an all-primary alcohol ZDDP compound that contributes 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 300 ppmw to 700 ppmw of zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

[0032] 23. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19 and 21, wherein the one or more ZDDP compounds may be derived from one or more primary alkyl alcohols each having an alkyl group containing 3 to 8 carbon atoms.

[0033] 24. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20 and 22, wherein the one or more ZDDP compounds may be derived from one or more primary alkyl alcohols each having an alkyl group containing 3 to 8 carbon atoms.

[0034] 25. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21 and 23, wherein the alkyl group of the one or more primary alkyl alcohols may have a branch at the beta carbon relative to the hydroxyl group.

[0035] 26. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22 and 24, wherein the alkyl group of the one or more primary alkyl alcohols may have a branch at the beta carbon relative to the hydroxyl group.

[0036] 27. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23 and 25, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols selected from the group consisting of n-propanol, isopropanol, isobutanol, n-butanol, 2-butanol, n-pentanol, hexanol, methyl isobutyl carbinol, isohexanol, n-heptanol, isoheptanol, octanol, pentanol and 2-ethylhexanol.

[0037] 28. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24 and 26, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols selected from the group consisting of n-propanol, isopropanol, isobutanol, n-butanol, 2-butanol, n-pentanol, hexanol, methyl isobutyl carbinol, isohexanol, n-heptanol, isoheptanol, octanol, pentanol and 2-ethylhexanol.

[0038] 29. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25 and 27, wherein the one or more ZDDP compounds can be derived from two or more primary alkyl alcohols.

[0039] 30. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 and 28, wherein the one or more ZDDP compounds can be derived from two or more primary alkyl alcohols.

[0040] 31. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27 and 29, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols and one or more secondary alkyl alcohols in a molar ratio of 100:20 to 50:50.

[0041] 32. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30, wherein the one or more ZDDP compounds can be derived from one or more primary alkyl alcohols and one or more secondary alkyl alcohols in a molar ratio of 100:20 to 50:50.

[0042] 33. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29 and 31, wherein the one or more ZDDP compounds may have a zinc to phosphorus molar ratio of 1.08 to 1.2.

[0043] 34. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 and 32, wherein the one or more ZDDP compounds may have a zinc to phosphorus molar ratio of 1.08 to 1.2.

[0044] 35. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31 and 33, wherein the one or more dispersants may be an ashless type dispersant.

[0045] 36. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32 and 34, wherein the one or more dispersants may be an ashless type dispersant.

[0046] 37. A lubricating oil composition according to any one of statements 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33 and 35, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyisobutylene having a number average molecular weight of from about 350 g / mol to about 50,000 g / mol, or to about 5000 g / mol, or from about 500 g / mol to about 3000 g / mol as determined by GPC.

[0047] 38. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34 and 36, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyisobutylene having a number average molecular weight of from about 350 g / mol to about 50,000 g / mol, or to about 5000 g / mol, or from about 500 g / mol to about 3000 g / mol as determined by GPC.

[0048] 39. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35 and 37, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyamine or a hydroxylamine.

[0049] 40. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36 and 38, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from a polyamine or a hydroxylamine.

[0050] 41. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37 and 39, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), higher polyethyleneamine (PEA) homologs and mixtures thereof; or the one or more dispersants comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylaminehexamine (PEHA); or the one or more dispersants comprise at least one N-substituted polyisobutylene succinimide dispersant derived from PEA used alone or in combination with TEPA.

[0051] 42. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 and 40, wherein the one or more dispersants may comprise at least one N-substituted polyisobutylene succinimide dispersant derived from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), higher polyethyleneamine (PEA) homologs and mixtures thereof; or the one or more dispersants comprise at least one N-substituted polyisobutylene succinimide dispersant derived from pentaethylaminehexamine (PEHA); or the one or more dispersants comprise at least one N-substituted polyisobutylene succinimide dispersant derived from PEA used alone or in combination with TEPA.

[0052] 43. A lubricating oil composition according to any one of statements 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39 and 41, wherein the one or more dispersants can have 0.1 wt % to 5 wt % nitrogen; or 0.25 wt % to 3 wt % nitrogen; or 0.5 wt % to 2 wt % nitrogen, the wt % based on the total weight of the one or more dispersants.

[0053] 44. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40 and 42, wherein the one or more dispersants may have 0.1 wt % to 5 wt % nitrogen; or 0.25 wt % to 3 wt % nitrogen; or 0.5 wt % to 2 wt % nitrogen, the wt % being based on the total weight of the one or more dispersants.

[0054] 45. A lubricating oil composition according to any one of statements 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41 and 43, wherein the one or more dispersants may 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 moieties per polyisobutylene (PIB) polymer; or about 1.1 and about 1.8 succinic moieties per PIB polymer.

[0055] 46. ​​A lubricating oil composition according to any of statements 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42 and 44, wherein the one or more dispersants may 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 moieties per polyisobutylene (PIB) polymer; or about 1.1 and about 1.8 succinic moieties per PIB polymer.

[0056] 47. A lubricating oil composition according to any one of statements 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43 and 45, wherein each of the one or more dispersants can have a TBN of about 10 mg KOH / g to about 65 mg KOH / g on an oil-free basis as measured by the method of ASTM D2896.

[0057] 48. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, and 46, wherein each of the one or more dispersants may have a TBN of about 10 mg KOH / g to about 65 mg KOH / g on an oil-free basis as measured by the method of ASTM D2896.

[0058] 49. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45 and 47, wherein the TBN contribution of the total dispersant to the TBN of the lubricating oil composition may be at least 0.79 mg KOH / g; or at least 0.85 mg KOH / g; or from 0.85 mg KOH / g to 5 mg KOH / g; or from 0.9 mg KOH / g to 2.5 mg KOH / g.

[0059] 50. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46 and 48, wherein the TBN contribution of the total dispersant to the TBN of the lubricating oil composition may be at least 0.79 mg KOH / g; or at least 0.85 mg KOH / g; or from 0.85 mg KOH / g to 5 mg KOH / g; or from 0.9 mg KOH / g to 2.5 mg KOH / g.

[0060] 51. A lubricating oil composition according to any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47 and 49, wherein the one or more dispersants may comprise at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, phosphorus compounds and mixtures thereof; or the one or more dispersants comprise at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0061] 52. A lubricating oil composition according to any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48 and 50, wherein the one or more dispersants may comprise at least one dispersant post-treated by reaction with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, phosphorus compounds and mixtures thereof; or the one or more dispersants comprise at least one dispersant post-treated by reaction with boron and maleic anhydride.

[0062] 53. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49 and 51, wherein the one or more dispersants are a mixture of at least one post-treated dispersant and at least one non-post-treated dispersant.

[0063] 54. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, and 52, wherein the one or more dispersants are a mixture of at least one post-treated dispersant and at least one non-post-treated dispersant.

[0064] 55. The lubricating oil composition of any one of clauses 1 to 4, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, and 53, wherein the amount of the one or more dispersants may be from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 1 wt % to about 10 wt %, or from about 1 wt % to about 8 wt %, or from about 1 wt % to about 7 wt %, based on the total weight of the lubricating oil composition.

[0065] 56. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, and 54, wherein the amount of the one or more dispersants may be from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 1 wt % to about 10 wt %, or from about 1 wt % to about 8 wt %, or from about 1 wt % to about 7 wt %, based on the total weight of the lubricating oil composition.

[0066] 57. The lubricating oil composition of any one of statements 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 and 55, further comprising at least one additive selected from the group consisting of a dispersant, an antioxidant, an antiwear agent, a defoaming agent, a molybdenum-containing compound, a titanium-containing compound, a phosphorus-containing compound, a pour point depressant and a diluent oil.

[0067] 58. The lubricating oil composition of any one of clauses 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54 and 56, further comprising at least one additive selected from the group consisting of a dispersant, an antioxidant, an antiwear agent, a defoaming agent, a molybdenum-containing compound, a titanium-containing compound, a phosphorus-containing compound, a pour point depressant and a diluent oil.

[0068] 59. The lubricating oil composition of any one of statements 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, 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.

[0069] 60. The lubricating oil composition of any one of statements 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 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.

[0070] 61. A method of reducing engine sludge of an internal combustion engine, the method comprising adding to the engine a lubricating oil composition according to any one of statements 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 and operating the engine.

[0071] 62. A method of reducing engine sludge of an internal combustion engine, the method comprising adding to the engine a lubricating oil composition according to any one of statements 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 and 60 and operating the engine.

[0072] 63. A method of improving the fuel economy and / or piston cleanliness performance of an engine and / or vehicle, the method comprising the step of providing to the engine and / or vehicle a lubricant composition as described in any one of statements 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.

[0073] 64. A method of improving the fuel economy and / or piston cleanliness performance of an engine and / or vehicle, the method comprising the step of providing to the engine and / or vehicle a lubricant composition as described in any one of statements 5 to 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 and 60.

[0074] The following definitions of terms are provided to clarify the meaning of certain terms as used herein.

[0075] The terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricating composition", "lubricating composition", "fully formulated lubricant composition", "lubricant", "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "motor oil" and "motor lubricant" are considered to be fully interchangeable synonymous terms referring to a finished lubricating product comprising a major base oil plus a minor additive composition.

[0076] 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," "motor oil concentrate" are considered to be fully interchangeable synonymous terms and refer to that portion of a lubricating oil composition that excludes the bulk base oil stock blend. The additive package may or may not include a viscosity index improver or a pour point depressant.

[0077] The term "overbased" relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates and / or phenolates, in which the content of the metal exceeds the stoichiometric amount. Such salts may have a conversion level exceeding 100% (i.e., they may contain 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and may be salts of organic sulfuric acid, carboxylic acid, salicylic acid and / or phenol.

[0078] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a hydrocarbon substituent containing one or more halogen groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furanyl groups, imidazolyl groups, oxygen and nitrogen substitutions, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the hydrocarbyl group.

[0079] As used herein, the term "alkylene substituent" or "alkylene group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule at two positions in the molecule through carbon atoms and has predominantly hydrocarbon characteristics. Each alkylene group is independently selected from a divalent hydrocarbon substituent, and a substituted divalent hydrocarbon substituent containing the following: a halo group, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, a hydroxyl group, an alkoxy group, a thiol group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, oxygen and nitrogen, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the alkylene group.

[0080] Unless expressly stated otherwise, as used herein, the term "percent by weight" refers to the percentage of the component by weight of the entire composition.

[0081] The terms "soluble", "oil-soluble" or "dispersible" as used herein may, but do not necessarily, mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in oil in all proportions. However, the aforementioned terms do mean that they are, for example, soluble, suspendable, dissolvable or stably dispersible in oil to a sufficient extent to exert their intended effect in the environment in which the oil is employed. In addition, if desired, the additional incorporation of other additives may also allow the incorporation of higher levels of a particular additive.

[0082] As employed herein, the term "TBN" is used to denote the Total Base Number in mg KOH / g as measured by the method of ASTM D2896 or ASTM D4739 or DIN 51639-1.

[0083] As employed herein, the term "alkyl" refers to a straight chain, branched chain, cyclic and / or substituted saturated chain moiety having from about 1 to about 100 carbon atoms.

[0084] As employed herein, the term "alkenyl" refers to a straight chain, branched, cyclic and / or substituted unsaturated chain moiety of about 3 to about 10 carbon atoms.

[0085] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds which may include alkyl, alkenyl, alkaryl, amino, hydroxy, alkoxy, halogen substituents and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0086] The lubricant of this specification, the combination of components or a single component can be suitable for use in various types of internal combustion engines. Suitable engine types can include but are not limited to heavy-duty diesel engines, passenger cars, light diesel engines, medium-speed diesel engines or marine engines. The internal combustion engine can be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a mixed diesel / biofuel fuel engine, a mixed gasoline / biofuel fuel engine, an alcohol fuel engine, a mixed gasoline / alcohol fuel engine, a compressed natural gas (CNG) fuel engine or a mixture thereof. The diesel engine can be a compression ignition engine. The gasoline engine can be a spark ignition engine. The internal combustion engine can also be used in combination with a power source or a battery power source. The engine constructed in this way is generally referred to as a hybrid engine. The internal combustion engine can be a 2-stroke, a 4-stroke or a rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, low-load diesel engines and motorcycles, automobiles, locomotives and truck engines.

[0087] The internal combustion engine can contain one or more components of aluminum alloy, lead, tin, copper, cast iron, magnesium, ceramic, stainless steel, composite and / or its mixture. The component can be coated with, for example, diamond-like carbon coating, lubricating coating, phosphorus-containing coating, molybdenum-containing coating, graphite coating, nanoparticle-containing coating and / or its mixture. The aluminum alloy can include aluminum silicate, aluminum oxide or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is intended to be synonymous with "aluminum composite material" and describes a component or surface comprising aluminum and another component that mixes or reacts with each other at a microscopic or near-microscopic level, regardless of its specific structure. This will include any conventional alloy having a metal other than aluminum and a composite or alloy-like structure (such as having a ceramic-like material) having a non-metallic element or compound.

[0088] Regardless of sulfur, phosphorus or sulfated ash (ASTM D-874) content, the lubricating oil composition for internal combustion engines can be suitable for any engine lubricant. The sulfur content of the engine oil lubricant can be about 1 weight % or less, or about 0.8 weight % or less, or about 0.5 weight % or less, or about 0.3 weight % or less, or about 0.2 weight % or less. In one embodiment, the sulfur content can be in the range of about 0.001 weight % to about 0.5 weight %, or about 0.01 weight % to about 0.3 weight %. The phosphorus content can be about 0.2 weight % or less, or about 0.1 weight % or less, or about 0.06 weight % or about 0.2 weight %. In one embodiment, the phosphorus content can be about 500ppmw to about 1250ppmw, or about 600ppmw to about 1200ppmw. The total sulfated ash content can be about 2 wt % or less, or about 1.5 wt % or less, or about 1.1 wt % or less, or about 1 wt % or less, or about 0.8 wt % or less, or about 0.5 wt % or less. In one embodiment, the sulfated ash content can be about 0.05 wt % to about 0.9 wt %, or about 0.1 wt % or about 0.2 wt % to about 0.45 wt %. In another embodiment, the sulfur content can be about 0.4 wt % or less, the phosphorus content can be about 0.12 wt % or less, and the sulfated ash can be about 1 wt % or less. In another embodiment, the sulfur content can be about 0.3 wt % or less, the phosphorus content can be about 0.11 wt % or less, and the sulfated ash can be about 0.8 wt % or less.

[0089] In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt % or less, (ii) a phosphorus content of about 0.1 wt % or less, and (iii) a sulfated ash content of about 1.5 wt % or less.

[0090] In one embodiment, the lubricating oil composition is suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel internal combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for use in a 2-stroke or 4-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 a marine-suitable engine oil (e.g., greater than about 40 TBN in a marine-suitable engine oil).

[0091] In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels, such as fuels containing from about 1 to about 5% sulfur.On-highway vehicle fuels contain about 15 ppmw sulfur (or about 0.0015% sulfur).

[0092] Low speed diesel engines generally refer to marine engines, medium speed diesel engines generally refer to railway locomotives, and high speed diesel engines generally refer to highway vehicles. The lubricating oil composition may be applicable to only one or all of these types.

[0093] In addition, the lubricants of the present description may be adapted to 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-4Plus, CI-4, APISG, 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 original equipment manufacturer specifications, such as Dexos 1. TM 、Dexos2 TM, MB-Approval229.1, 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-01FE, Longlife-04, Longlife-12FE, Longlife-14FE+, Longlife-17FE+, Porsche A40, C30, Peugeot Automobiles B712290, 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 9.55535G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specification not mentioned herein. In some embodiments for passenger car engine 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.

[0094] Other hardware may not be suitable for use with the disclosed lubricants. "Functional fluid" is a term that covers a variety of fluids, including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids including tractor hydraulic fluids, some gear oils, power steering fluids, fluids for wind turbines, compressors, some industrial fluids and fluids associated with driveline components. It should be noted that within each of these fluids, such as, for example, within automatic transmission fluids, there are various different types of fluids because various transmissions have different designs, which results in the need for fluids with significantly different functional characteristics. In contrast to this is the term "lubricating fluid," which is not used to generate or transmit power.

[0095] With regard to tractor hydraulic fluids, for example, these fluids are general-purpose products used for all lubricant applications in tractors other than lubricating the engine. These lubrication applications can include lubrication of gearboxes, power take-offs and clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

[0096] When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, when the fluid heats up during operation, the coefficient of friction of the fluid tends to decrease due to temperature effects. It is important that the tractor hydraulic fluid or automatic transmission fluid maintains its high coefficient of friction at elevated temperatures, otherwise the brake system or automatic transmission may fail. This is not a function of the engine oil.

[0097] Tractor fluids, and for example Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO), can combine the performance of engine oil with the performance of transmission, differential, final drive planetary gear, wet brake and hydraulic. Although many additives used to formulate UTTO or STUO fluids are similar in function, these additives may have harmful effects if not properly added. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specifically designed to eliminate wet brake noise may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor or lubricating, is designed to meet specific and stringent manufacturer requirements.

[0098] The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. The present disclosure provides novel lubricating oil blends formulated for use as 2T and / or 4T motorcycle crankcase lubricants. Embodiments of the present disclosure can provide lubricating oils suitable for crankcase applications and having improvements in the following features: aspiration, alcohol fuel compatibility, oxidation resistance, anti-wear performance, biofuel compatibility, defoaming properties, friction reduction, fuel economy, pre-ignition prevention, rust prevention, sludge and / or smoke dispersibility, piston cleanliness, deposit formation, and water tolerance.

[0099] The engine oils of the present disclosure can be formulated by adding one or more additives (as described in detail below) to a suitable base oil formulation. The additives can be combined with the base oil in the form of an additive package (or concentrate) or, alternatively, can be combined with the base oil (or a mixture of the two) alone. Based on the additives added and their corresponding proportions, the fully formulated engine oil can exhibit improved performance characteristics.

[0100] Other details and advantages of the present disclosure will be partially set forth in the following description, and / or can be understood through the practice of the present disclosure. The details and advantages of the present disclosure can be realized and obtained by the elements and combinations specifically pointed out in the appended claims. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and do not limit the present disclosure as claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 A graph of the contribution of the amount of zinc (Zn) provided by one or more ZDDP compounds to the lubricating oil composition, in weight percent, multiplied by the total base number (TBN) of the one or more dispersants to the TBN of the lubricating oil composition versus average engine sludge.

[0102] Figure 2 A graph of the contribution of the amount of phosphorus (P) provided by one or more ZDDP compounds to the lubricating oil composition in weight percent multiplied by the total base number (TBN) of one or more dispersants to the TBN of the lubricating oil composition versus average engine sludge. DETAILED DESCRIPTION

[0103] The present disclosure relates to lubricating oil compositions with reduced engine deposits. Specifically, the present disclosure relates to lubricating oil compositions, and methods for improving the resistance of lubricating oils to deposits in engines or other mechanical parts lubricated by the lubricating oils. The lubricating oils of the present disclosure can be used as passenger car engine oil (PVEO) products, commercial vehicle engine oil (CVEO) products, or other applications where the lubricating oil is subjected to heat and oxidative conditions.

[0104] In one embodiment, the lubricating oil composition of the present invention comprises greater than 50 weight percent of a base oil of lubricating viscosity and an additive composition comprising: one or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants, wherein the amount of zinc (Zn) provided to the lubricating oil composition by the one or more ZDDP compounds multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor Zn*TBNDisp of at least about 0.06.

[0105] In another embodiment, the lubricating oil composition of the present invention comprises greater than 50 weight percent of a base oil of lubricating viscosity and an additive composition comprising: one or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants, wherein the amount of phosphorus (P) provided to the lubricating oil composition by the one or more ZDDP compounds multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor P*TBNDisp of at least about 0.051.

[0106] ZDDP has antioxidant and anti-wear functions. Without being bound by theory, it is believed that ZDDP is used as an oxidation inhibitor to minimize the formation of deposit precursors (such as hydroperoxides and free radicals). These substances are reactive, and they attack the hydrocarbon base oils and additives that constitute the lubricant to form sludge, resins, varnishes and hard deposits. Dispersants coordinate with ZDDP by keeping these entities suspended in the bulk lubricant. This not only obtains improved deposit control, but also minimizes abrasive wear and viscosity increase associated with the particles.

[0107] As discussed in detail below, lubricating oil compositions are tested according to the Sequence VH engine test. The Sequence VH test (ASTM D8256) is a test method for evaluating the control of engine deposits by automotive engine oils under operating conditions intentionally selected to accelerate deposit formation. The engine is a spark ignition engine fueled by gasoline and operated under low temperature, light load conditions. One of the measurements included in the Sequence VH test is the average engine sludge. The cleanliness of the engine is measured via the sludge index, whereby a higher score demonstrates an increased engine cleanliness.

[0108] In one embodiment, when an engine oil is formulated with an additive composition characterized by a Zn*TBNDisp multiplication factor of at least about 0.06 and one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.071 weight percent zinc based on the total weight of the lubricating oil composition, there is improved resistance to engine deposits. This improvement is seen in engine oil formulations lacking the described characteristics.

[0109] In another embodiment, when an engine oil is formulated with an additive composition characterized by a Zn*TBNDisp multiplication factor of at least about 0.06 and the TBN contribution of the one or more dispersants to the TBN of the lubricating oil composition is at least 0.79 mg KOH / g, there is improved resistance to engine deposits. This improvement is seen in engine oil formulations lacking the described characteristics.

[0110] In another embodiment, when an engine oil is formulated with an additive composition characterized by a P*TBNDisp multiplication factor of at least about 0.051 and one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.065 wt. % P based on the total weight of the lubricating oil composition, there is improved resistance to engine deposits. This improvement is seen in engine oil formulations lacking the described characteristics.

[0111] In a further embodiment, when an engine oil is formulated with an additive composition characterized by a P*TBNDisp multiplication factor of at least about 0.051 and the TBN contribution of the one or more dispersants to the TBN of the lubricating oil composition is at least 0.79 mg KOH / g, there is improved resistance to engine deposits. This improvement is seen in engine oil formulations lacking the described characteristics.

[0112] Base oil

[0113] The base oil used in the lubricating oil composition herein can be selected from any one of the base oils in Group IV specified in the American Petroleum Institute (API) Base Oil Interchangeability Guide. The five base oil groups are shown in Table 1 below:

[0114] Table 1

[0115]

[0116] Class I, Class II and Class III are mineral oil processing raw materials.Class IV base oil contains real synthetic molecular species, and these synthetic molecular species are prepared by the polymerization of olefinically unsaturated hydrocarbons.Many Class V base oils are also real synthetic products, and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyvinyl ethers and / or polyphenylene ethers etc., but can also be naturally occurring oils, such as vegetable oils.It should be noted that although Class III base oil is derived from mineral oil, the strict processing of these fluid experiences causes their physical properties to be very similar to some real synthetic oils, such as PAO.Therefore, the oil derived from Class III base oil can be called synthetic fluid in industry.The II+ class can include high viscosity index Class II.

[0117] The base oil used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined and re-refined oils and mixtures thereof.

[0118] Unrefined oils are those derived from natural, mineral or synthetic sources with little or no further purification. Refined oils are similar to unrefined oils, except that they have been subjected to one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Refining to edible quality oils may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0119] Re-refined oils are also called reclaimed oils or reprocessed oils. Similar to refined oils, these oils are obtained using the same or similar processes. Typically these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0120] Mineral oil can comprise the oil obtained by drilling or the oil from plant and animal or their any mixture.For example, this type of oil can include but not limited to castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricating oil, such as liquid petroleum and solvent-treated or acid-treated paraffin, cycloalkane or mixed paraffin-cycloalkane type mineral lubricating oil.If necessary, this type of oil can be partially or completely hydrogenated.The oil deriving from coal or shale can also be applicable.

[0121] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomeric or copolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), 1-decene trimers or oligomers, such as poly(1-decene), such materials are generally referred to as alpha-olefins, and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof or mixtures thereof. Polyalpha-olefins are typically hydrogenated materials.

[0122] Other synthetic lubricating oils include polyol esters, diesters, liquid esters (e.g., diethyl esters of toluene phosphate, trioctyl phosphate and decanephosphonic acid) or polytetrahydrofurans containing phosphoric acid. Synthetic oils can be produced by Fischer-Tropsch reaction and can generally be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In one embodiment, oil can be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

[0123] The major amount of base oil included in the lubricating composition may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition. In another embodiment, the major amount of base oil included in the lubricating composition may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition.

[0124] The amount of oil of lubricating viscosity present can be the balance remaining after subtracting the sum of the amounts of performance additives including viscosity index improvers and / or pour point depressants and / or other pre-treatment additives from 100 wt %. For example, the oil of lubricating viscosity that can be present in the finished fluid can be a major amount, such as greater than about 50 wt %, greater than about 60 wt %, greater than about 70 wt %, greater than about 80 wt %, greater than about 85 wt %, or greater than about 90 wt %.

[0125] Dispersants

[0126] The lubricating oil composition further comprises one or more dispersants. Dispersants are generally referred to as ashless dispersants because they do not contain ash-forming metals before being mixed into the lubricating oil composition, and they generally do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides, wherein the number average molecular weight of the polyisobutylene substituent as measured by GPC is in the range of about 350 g / mol to about 50,000 g / mol, or to about 5,000 g / mol, or about 500 g / mol to about 3,000 g / mol. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethylene amines).

[0127] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher polyethyleneamine (PEA) homologues such as pentaethylaminehexamine (PEHA), etc. In one embodiment, the amine is PEA used alone or in combination with TEPA.

[0128] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but predominantly oligomers having 6 or more nitrogen atoms per molecule, 2 or more primary amines and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogens per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt% (e.g., >32 wt%) total nitrogen and an equivalent weight of primary amine groups of 120 g to 160 g / equivalent.

[0129] In some processes, suitable polyamines are generally referred to as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, typically less than about 80%.

[0130] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (equivalent weight per primary amine equivalent is 115-112 grams) and a total nitrogen content of about 33-34 weight percent. A heavy fraction of PAM oligomers that is almost free of TEPA and contains only very little PEHA but contains primarily oligomers with greater than 6 nitrogens and more extensive branching can produce a dispersant with improved dispersibility.

[0131] In one embodiment, the one or more dispersants have 0.1 wt % to 5 wt % nitrogen; or 0.25 wt % to 3 wt % nitrogen; or 0.5 wt % to 2 wt % nitrogen, the wt % based on the total weight of the one or more dispersants.

[0132] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight as determined by GPC in the range of about 350 g / mol to about 50,000 g / mol, or to about 5000 g / mol, or from about 500 g / mol to about 3000 g / mol. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0133] In some embodiments, polyisobutylene (when included) can have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also referred to as 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 determined by GPC are suitable for use in embodiments of the present 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%.

[0134] HR-PIB with a number average molecular weight in the range of about 900 g / mol to about 3000 g / mol as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutylene in the presence of a non-chlorinated catalyst (such as boron trifluoride), as described in U.S. Patent No. 4,152,499 of Boerzel et al. and U.S. Patent No. 5,739,355 of Gateau et al. When used in the aforementioned hot olefin reaction, HR-PIB can increase the conversion rate in the reaction, and reduce the amount of sediment formed, due to the enhanced reactivity. Suitable methods are described in U.S. Patent No. 7,897,696.

[0135] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per PIB polymer; or between about 1.1 and about 1.8 succinic acid moieties per PIB polymer.

[0136] The % activity of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of US Patent No. 5,334,321.

[0137] The percent conversion of the polyolefin was calculated from the % activity using the equations in columns 5 and 6 of US Patent No. 5,334,321.

[0138] Unless otherwise indicated, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with number average molecular weights ranging from 180 g / mol to about 18,000 g / mol as calibration reference.

[0139] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as a polyPIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0140] Suitable dispersants may have a TBN of about 10 mg / KOH / g to about 65 mg / KOH / g on an oil-free basis, which is comparable to a TBN of about 5 mg / KOH / g to about 30 mg / KOH / g if measured on a sample of the dispersant containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0141] The TBN of the total dispersant contributes to the TBN of the lubricating oil composition of at least 0.79 mg KOH / g; or at least 0.85 mg KOH / g; or from 0.85 mg KOH / g to 5 mg KOH / g; or from 0.9 mg KOH / g to 2.5 mg KOH / g. TBN is measured by the method of D2896.

[0142] Suitable classes of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or are commercially available.

[0143] The hydrocarbyl part of the hydrocarbyl-dicarboxylic acid or anhydride of component A) may alternatively be derived from ethylene-alpha-olefin copolymers. These copolymers contain a plurality of ethylene units and a plurality of one or more C3-C 10 α-olefin units. C3-C 10 The α-olefin unit may include a propylene unit.

[0144] One class of suitable dispersants may be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0145] A suitable class of dispersants may be high molecular weight esters or half ester amides.

[0146] Suitable dispersants may also be post-treated by conventional methods by reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. Preferably, the dispersant is post-treated with boron and maleic anhydride. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0147] The one or more dispersants can be a mixture of at least one post-treated dispersant and at least one non-post-treated dispersant. The weight ratio of the post-treated dispersant to the non-post-treated dispersant can be about 5:1 to about 1:15; or about 4:1 to about 1:10.

[0148] In addition to carbonate and boric acid post-treatments, both compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27 to 29 of U.S. Patent No. 5,241,003, incorporated herein by reference. Such treatments include treatment with:

[0149] Inorganic phosphorous acid or dehydrates (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980);

[0150] Organophosphorus compounds (e.g., U.S. Pat. No. 3,502,677);

[0151] Phosphorus pentasulfide;

[0152] Boron compounds such as those mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387);

[0153] Carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386);

[0154] Epoxides, polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495);

[0155] Aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530);

[0156] Carbon disulfide (e.g., U.S. Pat. No. 3,256,185);

[0157] Glycidol (e.g., U.S. Pat. No. 4,617,137);

[0158] Urea, thiourea or guanidine (eg, U.S. Pat. Nos. 3,312,619; 3,865,813; and GB 1,065,595);

[0159] Organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent GB 2,140,811);

[0160] Alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569);

[0161] Diketene (e.g., U.S. Pat. No. 3,546,243);

[0162] Diisocyanates (e.g., U.S. Pat. No. 3,573,205);

[0163] Alkane sultones (e.g., U.S. Pat. No. 3,749,695);

[0164] 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675);

[0165] Sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639);

[0166] Cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);

[0167] Cyclic carbonates or thiocarbonates linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170);

[0168] Nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent GB 2,140,811);

[0169] Hydroxyl-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522);

[0170] lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460);

[0171] Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170);

[0172] Nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent GB 2,440,811);

[0173] Hydroxyl-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522);

[0174] lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460);

[0175] Cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459);

[0176] Hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; 4,713,189);

[0177] Oxidants (e.g., U.S. Pat. No. 4,379,064);

[0178] Combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 3,185,647);

[0179] Combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086; 3,470,098);

[0180] A combination of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564);

[0181] Combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307);

[0182] Combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);

[0183] Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086);

[0184] A combination of a hydroxyaliphatic carboxylic acid followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322);

[0185] A combination of a hydroxy aliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064); a combination of formaldehyde and phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724);

[0186] A combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191);

[0187] Combinations of inorganic acids or anhydrides of phosphorus or partial or complete sulfur analogs thereof with boron-containing compounds (e.g., U.S. Pat. No. 4,857,214);

[0188] Combinations of an organic diacid, then an unsaturated fatty acid, and then a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycolizing agent (e.g., U.S. Pat. No. 4,973,412);

[0189] Combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278);

[0190] Combinations of aldehydes and triazoles followed by boron compounds (e.g., U.S. Pat. No. 4,981,492);

[0191] Combinations of cyclic lactones and boron compounds (eg, US Pat. Nos. 4,963,275 and 4,971,711). The above-referenced patents are incorporated herein in their entirety.

[0192] One or more dispersants can be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Another amount of one or more dispersants that can be used can be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 10 wt %, or about 1 wt % to about 8 wt %, or about 1 wt % to about 7 wt %, based on the total weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants can be used in any desired ratio.

[0193] Zinc dialkyl dithiophosphate compounds

[0194] The lubricating oil compositions of the present disclosure used in internal combustion engines to reduce engine sludge contain an amount of one or more zinc dialkyl dithiophosphates (ZDDP compounds). The one or more ZDDP compounds can also help improve the friction and wear properties of the lubricating oil composition.

[0195] One or more ZDDP compounds can be present in the lubricating oil composition in an amount from about 0.01 wt % to about 15 wt %, or from about 0.01 wt % to about 10 wt %, or from about 0.05 wt % to about 5 wt %, or from about 0.1 wt % to about 3 wt %, or from about 0.1 wt % to about 1.5 wt %, based on the total weight of the lubricating oil composition.

[0196] The one or more ZDDP compounds may include ZDDP compounds derived from primary alkyl alcohols, secondary alkyl alcohols, or a combination of primary and secondary alkyl alcohols. The primary and secondary alkyl alcohols used to prepare the one or more ZDDP compounds may have an alkyl group including 1 to 20 carbon atoms, or about 1 to 18 carbon atoms, or about 1 to about 16 carbon atoms, or 2 to 12 carbon atoms, or about 3 to about 8 carbon atoms. Preferably, the primary alkyl alcohol has a branch at the beta carbon relative to the hydroxyl group.

[0197] For example, an alcohol having a branch at the β carbon will have the branch at the second carbon from the oxygen atom of the hydroxyl group.

[0198]

[0199] Suitable examples of primary and secondary alkyl alcohols for preparing one or more ZDDP compounds can be selected from the group consisting of n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, n-pentanol, pentanol, hexanol, methyl isobutyl carbinol, isohexanol, n-heptanol, isoheptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, and 2-ethylhexanol.

[0200] The molar ratio of primary alkyl alcohol to secondary alkyl alcohol used to prepare the one or more ZDDP compounds in the lubricating oil composition can be about 1:5 to 2: 1. The one or more ZDDP compounds can 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, the one or more ZDDP compounds can be overbased with zinc oxide.

[0201] In some embodiments, the additive composition may include at least two different zinc dialkyl dithiophosphate compounds. The two alkyl groups on the zinc dialkyl dithiophosphate compound may be the same or different.

[0202] In some embodiments, 100 mol% of the alkyl groups of one or more ZDDP compounds may be derived from one or more primary alcohol groups. In some embodiments, 100 mol% of the alkyl groups 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 one or more all-primary alcohol ZDDP compounds that contribute 15 ppmw to 500 ppmw of zinc to the lubricating oil composition and one or more all-secondary alcohol ZDDP compounds that contribute 100 ppmw to 1000 ppmw of zinc to the lubricating oil composition based on the weight of the lubricating oil composition; or the mixture comprises one or more all-primary alcohol ZDDP compounds that contribute 100 ppmw to 400 ppmw of zinc to the lubricating oil composition and one or more all-secondary alcohol ZDDP compounds that contribute 300 ppmw to 700 ppmw of zinc to the lubricating oil composition based on the weight of the lubricating oil composition.

[0203] The alcohol suitable for producing one or more ZDDP compounds can be a primary alkyl alcohol, a secondary alkyl alcohol, or a mixture of a primary alcohol and a secondary alcohol. In one embodiment, the additive package comprises a ZDDP compound derived from an alcohol containing a primary alkyl group and another ZDDP compound derived from an alcohol containing a secondary alkyl group. In another embodiment, the ZDDP compound is derived from at least two secondary alcohols. The alcohol can contain any branched, cyclic or straight chain.

[0204] The one or more ZDDP compounds may be an oil-soluble salt of a dihydrocarbyl dithiophosphoric acid and may be represented by the formula:

[0205]

[0206] Wherein R5 and R6 can be identical or different alkyl groups, it contains 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 includes parts (such as alkyl and cycloalkyl parts). Therefore, the part can be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl, n-hexyl, isohexyl, 4-methyl-amyl, n-octyl, decyl, dodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylhexyl, nonadecyl, eicosyl, 2-ethylhexyl, cyclohexyl or methylcyclopentyl.

[0207] The average number of total carbon atoms per mole of phosphorus of the ZDDP compound can be calculated by dividing the sum of the carbon atoms in the four alkyl groups R5 and R6 provided to the ZDDP compound by the alcohol used to prepare the ZDDP compound. For example, for 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 two moles of phosphorus per mole of ZDDP gives an average total number of carbon atoms per mole of phosphorus of 9.

[0208] For compositions containing one or more ZDDP compounds, the average total number of carbon atoms per mole of phosphorus (ATCP) can be calculated from the alcohol used to prepare the ZDDP compound according to the following formula:

[0209] ATCP=2*[(mol% of alc1*number of C atoms in alc1)+(mol% of alc2*number of C atoms in alc2)

[0210] atoms) + (mol% in alc3 * number of C atoms in alc3) + ... etc.]

[0211] Wherein alc1, alc2 and alc3 each represent a different alcohol used to prepare the ZDDP compound, and mol% is the mole percentage of each alcohol present in the reaction mixture used to prepare the ZDDP compound. "Etc." means that if more than three alcohols are used to prepare the ZDDP compound, the formula can be expanded to include each alcohol present in the reaction mixture.

[0212] The average number of the total number of carbon atoms from both R5 and R6 in the ZDDP is greater than 2 carbon atoms per mole of phosphorus, and in one embodiment is within the range of greater than 4 to 40 carbon atoms, or greater than 6 to about 20 carbon atoms, and in one embodiment greater than 6 to about 16 carbon atoms, and in one embodiment from about 6 to about 15 carbon atoms, and in one embodiment from about 9 to about 15 carbon atoms, and in one embodiment about 12 carbon atoms per mole of phosphorus.

[0213] The zinc dialkyl dithiophosphate compound can be prepared according to known techniques by first forming a dialkyl dithiophosphoric acid (DDPA), typically by reaction of one or more alcohols, and then neutralizing the formed DDPA with a zinc compound. To prepare the zinc compound, any basic or neutral zinc compound can be used, but oxides, hydroxides and carbonates are most commonly used. The zinc dialkyl dithiophosphate of component (i) can be prepared by a process such as that generally described in U.S. Pat. No. 7,368,596.

[0214] In some embodiments, one or more ZDDP compounds may be present in the lubricating oil in an amount sufficient to provide from about 100 ppmw to about 1500 ppmw phosphorus, or from about 100 ppmw to about 1000 ppmw phosphorus, or from about 200 ppmw to about 1300 ppmw phosphorus, or from about 300 ppmw to about 1200 ppmw phosphorus, or from about 550 ppmw to about 1200 ppmw phosphorus, based on the total weight of the lubricating oil composition.

[0215] In some embodiments, one or more ZDDP compounds may be present in the lubricating oil in an amount sufficient to provide from about 10 ppmw zinc to about 1500 ppmw zinc, or from about 100 ppmw zinc to about 1300 ppmw zinc, or from about 600 ppmw zinc to about 1200 ppmw zinc, based on the total weight of the lubricating oil composition.

[0216] The use of one or more ZDDP compounds derived from a primary alkyl alcohol to a secondary alkyl alcohol in a molar ratio of about 100:0 to about 0:100 unexpectedly provides improved viscosity control in a variety of ZDDP compounds relative to the same lubricating oil composition except without the ZDDP compound. Specifically, the use of one or more ZDDP compounds derived from 100 mole % of one or more secondary alkyl alcohols and / or one or more ZDDP compounds derived from 100 mole % of one or more primary alkyl alcohols unexpectedly provides improved sludge resistance for improved viscosity control.

[0217] Additionally, one or more ZDDP compounds derived from all-secondary alkyl alcohols are used in a molar ratio of 100:0 to 0.2:1; or 10:1 to 0.4:1; or 6:1 to 0.75:1 to provide improved friction and / or wear results and / or viscosity control in the plurality of ZDDP compounds relative to lubricating oil compositions other than those without the ZDDP compounds.

[0218] The present invention may include a high basic ZDDP as a basic ZDDP. The term basic ZDDP or an equivalent expression is used herein to describe those zinc salts in which the metal substituent is present in a stoichiometrically greater amount than the phosphate radical. For example, a normal or neutral zinc dithiophosphate has two equivalents (i.e., 1 mole) of zinc per two equivalents (i.e., 2 moles) of zinc dithiophosphate, while a basic zinc diorganodithiophosphate has more than two equivalents of zinc per two equivalents of dithiophosphoric acid.

[0219] For example, the overbasing can be performed with a basic zinc compound (such as zinc oxide). The amount of basic zinc compound required to obtain the desired overbasing is not critical. The key factor is to provide enough zinc compound in the reaction mixture for the overbasing reaction. Although it is not absolutely necessary, it has been found that if a slightly excess of zinc compound is used than the amount required for the reaction, the reaction proceeds in a more satisfactory manner. The excess should be maintained at the minimum level necessary to remove a large amount of solids from the final product. As a general statement, the excess of zinc compound should not exceed 10% to 15% by weight.

[0220] Friction modifiers

[0221] The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary ammoniums, imides, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

[0222] Suitable friction modifiers may contain a hydrocarbyl group selected from a linear, branched or aromatic hydrocarbyl group or a mixture thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbyl group may be in the range of about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester or a diester or a (tri) glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative or a long-chain imidazoline.

[0223] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to oleophilic hydrocarbon chains. An example of an organic ashless, nitrogen-free friction modifier is generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0224] Amine friction modifiers can include amines or polyamines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and can contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0225] The amines and amides can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid or mono-, di- or tri-alkyl borate esters. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

[0226] The friction modifier may optionally be present in a range such as from about 0 wt % to about 10 wt %, or from about 0.01 wt % to about 8 wt %, or from about 0.1 wt % to about 4 wt %.

[0227] Antioxidants

[0228] In addition to one or more ZDDP compounds, the lubricating oil composition of the present invention may also optionally include one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphorus sulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0229] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further substituted with a hydrocarbyl group and / or a bridging group connected 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 and may include, for example, Irganox®, which may be purchased from BASF. TML-135 or the addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox 1,6-di-tert-butylphenol, available from Albemarle Corporation. TM 4716.

[0230] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent based on the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 weight percent to about 1.5 weight percent diarylamine and about 0.4 weight percent to about 2.5 weight percent high molecular weight phenol based on the final weight of the lubricating oil composition.

[0231] The example of suitable olefins that can be sulfurized to form sulfurized olefins includes propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or its mixture. In one embodiment, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or its mixture, and its dimer, trimer and tetramer are particularly suitable olefins. Alternatively, the olefin can be a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate) Diels-Alder adduct (Diels-Alder adduct).

[0232] Another class of sulphurized olefins includes sulphurized fatty acids and esters thereof. Fatty acids are usually obtained from vegetable oils or animal oils and usually contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0233] In another alternative embodiment, in addition to the phenolic and / or aminic antioxidants discussed above, the antioxidant composition also contains a platinum-containing antioxidant. When a combination of these three antioxidants is used, preferably, the ratio of phenolic antioxidant to aminic antioxidant to platinum-containing antioxidant is (0 to 2):(0 to 2):(0 to 1).

[0234] One or more antioxidants may be present in a range from about 0 wt % to about 20 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % of the lubricating oil composition.

[0235] Antiwear Agents

[0236] In addition to one or more ZDDP compounds, the lubricating oil composition of the present invention may optionally include one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; phosphates or salts thereof; phosphate esters; phosphites; phosphorus-containing carboxylates, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl)disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamates. Phosphorus-containing antiwear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A usable antiwear agent may be zinc dialkyl dithiophosphate.

[0237] Additional examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulphurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl)disulfides). The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the antiwear agent may include a citrate ester.

[0238] Antiwear agents may be present in a range of about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0239] Boron compounds

[0240] The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.

[0241] Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in US Pat. No. 5,883,057.

[0242] The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 wt %, about 0.01 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0243] Detergent

[0244] The lubricating oil composition may include one or more detergents. One or more detergents may be neutral, low alkaline or high alkaline detergents and mixtures thereof. Suitable detergent bases include benzoates, sulfur-containing benzoates, sulfonates, calixformates, salicylates, salicylates, carboxylic acids, phosphoric acid, monothiophosphoric acid and / or dithiophosphoric acid, alkylphenols, sulfur-coupled alkylphenol compounds or methylene bridged phenols. Suitable detergents and methods for their preparation are described in more detail in multiple patent disclosures, including U.S. Patent No. 7,732,390 and references cited therein.

[0245] One or more detergents may be formed from a detergent matrix salted with an alkali or another alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free.

[0246] Suitable detergents may include salts of petroleum sulfonic acids and long chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, sulfur-containing calcium phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium monothiophosphates and / or dithiophosphates, alkyl calcium phenates, sulfur-coupled alkyl calcium phenates, methylene-bridged calcium phenates, magnesium phenates, sulfur-containing magnesium phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and / or dithiophosphates, alkyl magnesium phenates, sulfur-coupled alkyl magnesium phenates, methylene-bridged magnesium phenates, sodium phenates, sulfur-containing sodium phenates, sodium sulfonates, sodium calixarates, sodium salixarates, salixarates), sodium salicylates, sodium carboxylates, sodium phosphates, sodium monothiophosphates and / or sodium dithiophosphates, sodium alkylphenols, sulfur-coupled sodium alkylphenol compounds, or methylene-bridged sodium phenols.

[0247] The one or more detergents may be overbased detergents. Such detergent additives may 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, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0248] The term "overbased" refers to metal salts, such as metal salts with sulfonic acids, carboxylic acids and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level exceeding 100% (i.e., they can contain 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and can be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0249] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or greater, or as other examples, about 225 mg KOH / gram or greater, or about 250 mg KOH / gram or greater, or about 300 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater.

[0250] Preferably, the one or more detergents comprise a highly basic calcium-containing detergent. Examples of suitable highly basic calcium-containing detergents include, but are not limited to, highly basic calcium phenates, highly basic sulfur-containing calcium phenates, highly basic calcium sulfonates, highly basic calcium calixarene alcohols, highly basic calcium salicylates, highly basic calcium salicylates, highly basic calcium carboxylates, highly basic calcium phosphates, highly basic monothiophosphoric acids and / or dithiophosphoric acids, highly basic calcium alkylphenols, highly basic sulfur-coupled alkylphenol calcium compounds, and highly basic methylene-bridged calcium phenates. Preferably, the highly basic calcium-containing detergent is a highly basic calcium sulfonate detergent.

[0251] Examples of other suitable overbased detergents include, but are not limited to, overbased magnesium phenoxides, overbased magnesium sulfur-containing phenoxides, overbased magnesium sulfonates, overbased magnesium calixarene alcohols, overbased magnesium salicylates, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenoxides, overbased sulfur-coupled alkylphenoxide magnesium compounds, or overbased methylene-bridged magnesium phenoxides.

[0252] The overbased detergent may have a metal to substrate ratio of 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1.

[0253] One or more detergents can be low alkalinity / neutral detergents, and their TBN is at most 175mg KOH / g, or at most 150mg KOH / g. Low alkalinity / neutral detergents can be formed by detergent bases salified with alkali or another alkaline earth metal (such as but not limited to calcium, magnesium, potassium, sodium, lithium, barium or its mixture). In some embodiments, detergent does not contain barium. Low alkalinity / neutral detergents can be selected from sulfonate, phenate or salicylate detergents. In some embodiments, low alkalinity / neutral detergents can be calcium-containing detergents or mixtures of calcium-containing detergents. In some embodiments, low alkalinity / neutral detergents can be calcium sulfonate detergents or calcium phenate detergents. In one embodiment, one or more detergents comprise a mixture of one or more low alkalinity / neutral calcium-containing detergents and one or more high alkalinity calcium-containing detergents.

[0254] The one or more detergents may comprise an overbased calcium-containing detergent and a low-based / neutral detergent which is a salt of an alkali metal or alkaline earth metal other than calcium.

[0255] The amount of calcium provided by the one or more calcium-containing detergents is greater than about 0.01 wt %; or greater than about 0.02 wt %; or up to about 0.25 wt %; or from about 0.010 wt % to about 0.25 wt %; or from about 0.02 wt % to about 0.20 wt %; or from about 0.02 wt % to about 0.15 wt %, wherein the amount is based on the total weight of the lubricating oil composition.

[0256] The low base / neutral detergent may provide calcium in an amount of at least 0.001 wt % of the calcium provided by the total detergent in the lubricating oil composition. In some embodiments, the low base / neutral detergent may provide calcium in an amount of at least 0.003 wt %, or 0.003 wt % to 0.05 wt % of the calcium provided by the total detergent in the lubricating oil composition.

[0257] In certain embodiments, the one or more low base / neutral detergents provide from about 1 ppmw to about 400 ppmw (by weight) of calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low base / neutral calcium-containing detergents provide from 1 ppmw to 350 ppmw of calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

[0258] In some embodiments, the detergent is effective to suspend deleterious products formed in the lubricating oil composition during engine use.

[0259] The detergent may be present from about 0 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 0.2 wt % to about 4 wt %, based on the total weight of the lubricating oil composition.

[0260] Molybdenum-containing components

[0261] The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides 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 dithiocarbamates, molybdenum dialkyl dithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamates.

[0262] Suitable examples of molybdenum compounds that may be used include commercial materials sold under the following trade names: such as Molyvan 822 from RT Vanderbilt Co., Ltd. TM 、Molyvan TM A. Molyvan2000 TM 、Molyvan 1055 TM and Molyvan 855 TM ; and Sakura-Lube available from Adeka Corporation TM and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entireties of which are incorporated herein by reference.

[0263] In addition, the molybdenum compound can be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, these compositions can provide molybdenum through molybdenum / sulfur complexes of basic nitrogen compounds, such as, for example, U.S. Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entire contents of which are incorporated herein by reference.

[0264] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds such as those of the formula Mo3S k L n Q z Those and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organic groups having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies in the range of 4 to 7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There may be a total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms in the organic groups of all ligands. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entirety of which is incorporated herein by reference.

[0265] The oil-soluble molybdenum compound is present in an amount sufficient to provide from about 0.5 ppmw to about 2000 ppmw, from about 1 ppmw to about 700 ppmw, from about 1 ppmw to about 550 ppmw, from about 5 ppmw to about 300 ppmw, or from about 20 ppmw to about 250 ppmw of molybdenum.

[0266] Compounds containing transition metals

[0267] In another embodiment, the oil-soluble compound can be a compound containing a transition metal or a metalloid. The transition metal can include, but is not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0268] In one embodiment, the oil-soluble transition metal-containing compound can function as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound can be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that can be used in the disclosed technology or can be used to prepare the oil-soluble materials of the disclosed technology are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxide, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, 2-ethylhexyl titanium; and other titanium compounds or complexes, including but not limited to titanium phenolate; titanium carboxylate, such as 2-ethyl-1-3-adipate titanium (IV) or titanium citrate or titanium oleate; and (triethanolamine) isopropoxide titanium (IV). Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkylbenzene sulfonates), or generally, the reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimerized or oligomeric forms, containing Ti--O--Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques readily known to those skilled in the art. It exists in solid or liquid form at room temperature, depending on the specific compound. It can also be provided in the form of a solution in a suitable inert solvent.

[0269] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly, or it can be reacted with any of a number of materials, such as (a) a polyamine-based succinimide / amide dispersant having free, condensable --NH functional groups; (b) components of a polyamine-based succinimide / amide dispersant, i.e., an alkenyl-(or alkyl-) succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by reacting a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols or fatty acids, and the product thereof can be used directly to impart Ti to the lubricant, or in addition, reacted with a succinic acid dispersant as described herein. As an example, 1 part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by mole) of polyisobutylene-substituted succinic anhydride at 140° C.-150° C. for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant and a polyethylene polyamine mixture (127 g + diluent oil) from a polyisobutylene-substituted succinic anhydride at 150° C. for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0270] Another titanium-containing compound can be a titanium alkoxide with a C6 to C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0271]

[0272] wherein n is an integer selected from 2, 3 and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or is represented by the formula:

[0273]

[0274] wherein m+n=4 and n is in the range of 1 to 3, R4 is an alkyl moiety having carbon atoms in the range of 1 to 8, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, or is represented by the following formula:

[0275]

[0276] wherein x is in the range of 0 to 3, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, and R4 is selected from H, or C6 to C 25A group consisting of carboxylic acid moieties.

[0277] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0278] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 ppmw to 3000 ppmw titanium (by weight), or from 25 ppmw to about 1500 ppmw titanium (by weight), or from about 35 ppmw to 500 ppmw titanium (by weight), or from about 50 ppmw to about 300 ppmw.

[0279] Viscosity Index Improver

[0280] The lubricating oil composition herein can also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers can include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers can include star polymers, and suitable examples are described in U.S. Publication No. 2012 / 0101017A1.

[0281] The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with amines, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0282] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improvers may be from about 0 wt.% to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, from about 0.1 wt.% to about 12 wt.%, or from about 0.5 wt.% to about 10 wt.% of the lubricating oil composition.

[0283] Other optional additives

[0284] Other additives may be selected to perform one or more functions required of the lubricating fluid.In addition, one or more of the mentioned additives may be multifunctional and provide functionality in addition to or different from the functionality specified herein.

[0285] Lubricating oil compositions according to the present disclosure may optionally include other performance additives. Other performance additives may be additives other than the specified additives of the present disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swell agents and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0286] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dithiothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0287] Suitable foam suppressors include silicon-based compounds such as siloxanes.

[0288] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.02 wt % to about 0.04 wt % based on the final weight of the lubricating oil composition.

[0289] Suitable rust inhibitors can be single compounds or compound mixtures having the characteristics of inhibiting corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors 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; and oil-soluble polycarboxylic acids including dimer acid and trimer acid, such as those produced by pine oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α, ω-dicarboxylic acids with a molecular weight ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecene succinic acid, and hexadecene succinic acid. Another type of acidic corrosion inhibitor available is a half ester of alkenyl succinic acid and alcohol (such as polyethylene glycol) having about 8 to about 24 carbon atoms in the alkenyl group. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.In some embodiments, the engine oil contains no rust inhibitors.

[0290] Rust inhibitors, if present, may be used in amounts sufficient to provide from about 0 wt % to about 5 wt %, from about 0.01 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt % based on the final weight of the lubricating oil composition.

[0291] In general, suitable crankcase lubricants may include an additive component within the ranges listed in the table below.

[0292] Table 2

[0293]

[0294] The percentages of each component 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 is made up of one or more base oils.

[0295] The additives used to formulate the compositions described herein may be blended into the base oil individually or in various subcombinations. However, it may be appropriate to blend all components simultaneously using an additive concentrate (ie, additives plus a diluent, such as a hydrocarbon solvent).

[0296] Example

[0297] The following examples are illustrative and non-limiting of the methods and compositions of the present disclosure. Other suitable modifications and adjustments of the various conditions and parameters commonly encountered in the art and apparent to those skilled in the art are within the spirit and scope of the present disclosure. All patents and publications cited herein are incorporated herein by reference in their entirety.

[0298] Each of the lubricating oil compositions contains a major amount of base oil and a basic conventional dispersant inhibitor (DI) package. The DI package contains conventional amounts of dispersants, anti-wear additives, antioxidants, friction modifiers, defoamers, process oils, viscosity index improvers and pour point depressants, as listed in Table 3. Specifically, the DI package contains a succinimide dispersant, a molybdenum-containing compound, an antioxidant and a defoamer. The major amount of base oil is a mixture of Group II and Group III base oils. The components that vary are indicated in the following table and in the discussion of the examples. Unless otherwise stated, all values ​​listed are expressed as weight percentages of the components (i.e., active ingredients plus diluent oil, if any) in the lubricating oil composition.

[0299] Table 3 – DI package composition range

[0300] Components weight% One or more antioxidants 0.5 to 2.5 One or more defoamers 0.001 to 0.05 One or more detergents 0.1 to 2.0 One or more dispersants See Table 5 Metallic Friction Modifiers 0 to 1.5 Metal-free friction modifiers 0 to 0.5 One or more pour point depressants 0 to 0.5 Processing oil 0.25 to 1.0 ZDDP See Table 5 Viscosity Modifiers 0 to 10.0

[0301] The lubricating oil compositions were tested according to the Sequence VH engine test. The Sequence VH test (ASTM D8256) is a test method used to evaluate the control of engine deposits by automotive engine oils under operating conditions intentionally selected to accelerate deposit formation. The engine was a spark ignition engine fueled by gasoline and operated under low temperature, light load conditions. A 2013 Ford 4.6L fuel injected eight cylinder gasoline engine with roller followers, coolant jacketed rocker covers and camshaft baffles was used.

[0302] The test duration was 216 hours and included 54 cycles, where each cycle consisted of three different operating phases, as shown in Table 4 below. A fuel containing a sludge precursor was used, and engine blowby was intentionally increased. The rocker cover jacket temperature was cycled.

[0303] Table 4 – Test parameters

[0304]

[0305] Assess sludge deposits on rocker covers, rocker cover guards, timing chain covers, oil pan guards, oil pans and valve covers.

[0306] One of the measurements included in the Sequence VH test is the average engine sludge. The cleanliness of the engine is measured via the sludge index, whereby a higher score demonstrates increased engine cleanliness. The oil passes the average engine sludge test at 7.01 minutes or more. The results of the average engine sludge test are given in Table 5 below.

[0307] Table 5

[0308]

[0309]

[0310] a) Contribution of the TBN of all dispersants to the TBN of the lubricating oil composition

[0311] b) Weight % phosphorus from ZDDP x TBN of total dispersant contribution to TBN of lubricating oil composition (P x TBNDisp - column 2 x column 4)

[0312] c) Contribution of weight % zinc from ZDDP x TBN of total dispersant to TBN of lubricating oil composition (Zn x TBNDisp - column 3 x column 4)

[0313] The data in Table 5 are plotted on Figure 1 The data in Table 5 and Figure 1The graph in demonstrates that lubricating oil compositions comprising: one or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants have improved cleanliness, wherein the amount of zinc (Zn) provided to the lubricating oil composition by the one or more ZDDP compounds, on a weight percent basis, multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor of Zn*TBNDisp weight percent of at least about 0.06. This is evident from the higher average engine sludge values ​​of Inventive Examples IE-1 through IE-7 when compared to the values ​​of Comparative Examples CE-1 through CE-4.

[0314] The data in Table 5 also demonstrate that lubricating oil compositions formulated to have a multiplication factor wt% Zn*TBNDisp of at least about 0.06 and an amount of zinc provided by the one or more ZDDP compounds of from 0.070 wt% to 0.11 wt% based on the total weight of the lubricating oil composition have improved cleanliness. This is evident from the higher average engine sludge values ​​of Inventive Examples IE-1 to IE-7 when compared to the values ​​of Comparative Examples CE-1 to CE-4.

[0315] Additionally, the data in Table 5 also demonstrates that lubricating oil compositions formulated to have a weight percent Zn*TBNDisp multiplication factor of at least about 0.06 and one or more dispersants having a TBN contribution of at least 0.79 mg KOH / g to the TBN of the lubricating oil composition have improved cleanliness. This is evident from the higher average engine sludge values ​​for Inventive Examples IE-1 through IE-7 when compared to the values ​​for Comparative Examples CE-1 through CE-4.

[0316] The data in Table 5 are also plotted on Figure 2 The data in Table 5 and Figure 2 The graph in demonstrates that lubricating oil compositions comprising: one or more zinc dialkyl dithiophosphates (ZDDP compounds) and one or more dispersants have improved cleanliness, wherein the amount of phosphorus (P) provided to the lubricating oil composition by the one or more ZDDP compounds, on a weight percent basis, multiplied by the total base number (TBN) of the one or more dispersants contributes to the TBN of the lubricating oil composition by a multiplication factor P*TBNDisp weight percent of at least about 0.051. This is evident from the higher average engine sludge values ​​of Inventive Examples IE-1 through IE-7 when compared to the values ​​of Comparative Examples CE-1 through CE-4.

[0317] Table 5 and Figure 2The data in also demonstrate that lubricating oil compositions formulated such that the weight percent P*TBNDisp multiplication factor is at least about 0.051 and one or more ZDDP compounds are present in an amount sufficient to provide greater than about 0.065 weight percent P based on the total weight of the lubricating oil composition have improved cleanliness. This is evident from the higher average engine sludge values ​​for Inventive Examples IE-1 through IE-7 when compared to the values ​​for Comparative Examples CE-1 through CE-4.

[0318] In addition, Table 5 and Figure 2 The data in also demonstrate that lubricating oil compositions formulated to have a weight percent P*TBNDisp multiplication factor of at least about 0.051 and one or more dispersants having a TBN contribution of at least 0.79 mg KOH / g to the TBN of the lubricating oil composition have improved cleanliness. This is evident from the higher average engine sludge values ​​for Inventive Examples IE-1 through IE-7 when compared to the values ​​for Comparative Examples CE-1 through CE-4.

[0319] After considering the practice of this specification and the embodiments disclosed herein, other embodiments of the present disclosure will be apparent to those skilled in the art. As used throughout the specification and claims, "one / one (kind) (an)" and / or "one / one (kind) (an)" and / or "described" may refer to one or more than one. Unless otherwise indicated, all numerals representing quantity, ratio, percentage or other numerical values ​​are to be understood as being modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in this specification and claims are approximate values ​​that may vary depending on the desired properties attempted to be obtained by the present disclosure. Minimally, and without attempting to limit the scope of the application of the doctrine of equivalents to the claims, each numerical parameter should at least be interpreted according to the number of reported significant figures and by applying general rounding techniques.

[0320] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters disclosed herein.

[0321] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range with the same number of significant figures. Thus, for example, a range of 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of such values.

[0322] It should be further understood that each lower limit of each scope disclosed herein should be interpreted as being disclosed in combination with each upper limit of each scope disclosed herein for the same component, compound, substituent or parameter and each specific value in each scope. Therefore, the disclosure should be interpreted as being disclosed by combining each lower limit of each scope with each upper limit of each scope or with each specific value in each scope, or by combining each upper limit of each scope with each specific value in each scope. That is, it should also be further understood that any scope between the endpoint values ​​in a wide range is also discussed herein. Therefore, the scope of 1 to 4 also means the scope of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0323] In addition, a specific amount / value of a component, compound, substituent or parameter disclosed in this specification or the examples should be interpreted as a disclosure of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of a range for the same component, compound, substituent or parameter disclosed elsewhere in this disclosure to form a range for that component, compound, substituent or parameter.

Claims

1. A lubricating oil composition comprising more than 50% by weight of a base oil of lubricating viscosity and an additive composition, wherein the additive composition comprises: one or more zinc dialkyl dithiophosphates (ZDDP compounds), one or more calcium-containing detergents, and one or more dispersants, wherein the one or more dispersants consist of a dispersant derived from polyisobutylene succinic anhydride (PIBSA), The one or more calcium-containing detergents are present in an amount to provide 0.01 wt % calcium to 0.25 wt % calcium to the lubricating oil composition, and wherein the amount of zinc (Zn) provided to the lubricating oil composition by the one or more ZDDP compounds, on a weight percent basis, multiplied by the total base number (TBN) of the one or more dispersants derived from the PIBSA contributes to the TBN of the lubricating oil composition is a Zn*TBNDisp multiplication factor, and the Zn*TBNDisp multiplication factor is at least 0.

06.

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

07.

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

4. The lubricating oil composition of claim 1, wherein the Zn*TBNDisp multiplication factor is at least 0.06 and the TBN of the one or more dispersants contributes at least 0.79 mg KOH / g to the TBN of the lubricating oil composition.

5. A lubricating oil composition comprising greater than 50% by weight of a base oil of lubricating viscosity and an additive composition, wherein the additive composition comprises: one or more zinc dialkyl dithiophosphates (ZDDP compounds), one or more calcium-containing detergents, and one or more dispersants, wherein the one or more dispersants consist of a dispersant derived from polyisobutylene succinic anhydride (PIBSA), The one or more calcium-containing detergents are present in an amount to provide 0.01 wt % calcium to 0.25 wt % calcium to the lubricating oil composition, and wherein the amount of phosphorus (P) provided to the lubricating oil composition by the one or more ZDDP compounds, on a weight percent basis, multiplied by the total base number (TBN) of the one or more dispersants derived from the PIBSA contributes to the TBN of the lubricating oil composition is a P*TBNDisp multiplication factor, and the P*TBNDisp multiplication factor is at least 0.

051.

6. The lubricating oil composition according to claim 5, wherein the P*TBNDisp multiplication factor is from 0.06 to 0.

5.

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

8. The lubricating oil composition of claim 5, wherein the P*TBNDisp multiplication factor is at least 0.051 and the TBN of the one or more dispersants contributes at least 0.79 mg KOH / g to the TBN of the lubricating oil composition.

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

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

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

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

13. The lubricating oil composition of claim 11, wherein the mixture comprises an all-primary alcohol ZDDP compound that contributes 15 ppmw to 500 ppmw zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 100 ppmw to 1000 ppmw zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

14. The lubricating oil composition of claim 12, wherein the mixture comprises an all-primary alcohol ZDDP compound that contributes 15 ppmw to 500 ppmw zinc to the lubricating oil composition and an all-secondary alcohol ZDDP compound that contributes 100 ppmw to 1000 ppmw zinc to the lubricating oil composition, based on the weight of the lubricating oil composition.

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

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

17. The lubricating oil composition of claim 1, wherein the TBN of all of the dispersants contributes at least 0.79 mg KOH / g to the TBN of the lubricating oil composition.

18. The lubricating oil composition of claim 5, wherein the TBN of all of the dispersants contributes at least 0.79 mg KOH / g to the TBN of the lubricating oil composition.

19. The lubricating oil composition of claim 1, wherein the one or more dispersants derived from PIBSA are a mixture of at least one post-treated dispersant and at least one non-post-treated dispersant.

20. The lubricating oil composition of claim 5, wherein the one or more dispersants derived from PIBSA are a mixture of at least one post-treated dispersant and at least one non-post-treated dispersant.

21. A method of reducing engine sludge of an internal combustion engine, the method comprising adding the lubricating oil composition of claim 1 to the engine and operating the engine, wherein the lubricating oil composition provides an average engine sludge test result of 7.01 minutes or greater, the sludge test standard being ASTM D8256.

22. A method of reducing engine sludge of an internal combustion engine, the method comprising adding the lubricating oil composition of claim 5 to the engine and operating the engine, wherein the lubricating oil composition provides an average engine sludge test result of 7.01 minutes or greater, the sludge test standard being ASTM D8256.

23. A method for improving the fuel economy performance and / or piston cleanliness performance of an engine and / or a vehicle, the method comprising the step of providing the lubricating oil composition according to claim 1 to the engine and / or the vehicle.

24. A method for improving the fuel economy performance and / or piston cleanliness performance of an engine and / or a vehicle, the method comprising the step of providing the lubricating oil composition according to claim 5 to the engine and / or the vehicle.

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